CN1059684A - Laminated molded article and manufacture method thereof - Google Patents

Abstract

The invention provides a kind of laminated molded article, it is by forming with the lower part: (a) sandwich layer of being made up of synthetic resin; (b) be located on this sandwich layer, by with a kind of grafted monomers modification the intermediate layer (II) formed of improved polyalkene; (c) be located at top layer on this intermediate layer (II), that form by a kind of polymer, that can be banded by fluffing in case of necessity.This lamination formed body has excellent hear resistance, cold resistance, antifriction consumption, traumatic resistance, oil resistivity, solvent resistance.

Description

Laminated molded article and manufacture method thereof

The present invention is relevant lamination formed body and manufacture method thereof, specifically, is about soft lamination formed body with good hear resistance, cold resistance, oil resistivity, solvent resistance, wear resistance and traumatic resistance and manufacture method thereof.

People know, always are to protect solid forming product surface with the top layer of synthetic resin, or as the formed body of having decorated and having printed, will form the lamination formed body on the central core of being made by synthetic resin by the skin lay-up that other synthetic resin is made.

This lamination formed body, be to adopt vacuum forming method, synthetic resin sheet material is adsorbed on injection molding forming with being shaped in advance on the mould intracavity wall of metal die, the synthetic resin that will be in the plasticization state that flows then injects the die cavity inner mold and is shaped and obtains, and mainly is widely used in the internal and external ornamental part of automobile and building materials etc.

The advantage of this formed body is as epidermal area, as using the material that has literal and pattern etc. in advance, just needn't draw after the solid forming product are shaped again.

But, always synthetic resin sheet material or the film that uses as the top layer is to use polyvinyl chloride etc., and the problem that skin-material always exists is, the attractability during vacuum forming is poor, the complicated more shaping of the three-dimensional shape of formed body is difficult more, the corner place often cracks or form wrinkle etc. at some position.In addition, duplicate the candy strip on the metal die mould intracavity wall face and the wrinkle that form also may not be good.Also have, the hear resistance of the epidermal area of polyvinyl chloride etc., cold resistance, oil resistivity, solvent resistance, wear resistance and traumatic resistance are all relatively poor.In addition, because of plasticizer oozes out, feel is not good enough yet when being used for the automobile inside trim.

The present invention puts forth effort on and solves above-mentioned each problem, and its objective is provides soft lamination formed body and the manufacture method thereof with good hear resistance, cold resistance, oil resistivity, solvent resistance, wear resistance and traumatic resistance.

Another object of the present invention provides and has both above-mentioned each superperformance, soft and have the lamination formed body and a manufacture method thereof of candy strip clearly.

The characteristics of the 1st kind of lamination formed body among the present invention are that sandwich layer and (second) made with synthetic resin by (first) place on this sandwich layer with polyolefin foam, the intermediate layer (I) that polyurethane foam body and thermoplastic elastic foams are made and (third) place process on this intermediate layer (I) from unsaturated carboxylic acid, the derivative of unsaturated carboxylic acid, the intermediate layer (II) that the improved polyalkene based elastomers of at least a kind of grafted monomers graft modification selecting in the colony that unsaturated epoxy monomer and unsaturated carboxylic monomer form is made and (fourth) place on this intermediate layer (II) from polyamide, the epidermal area that at least a kind of polymer selecting in the colony that polyurethane and polyester form is made constitutes.

The 1st kind of lamination molded article production method among the present invention is characterised in that, through following operation, the i.e. 3 synusia material preheatings that constitute of the epidermal area made of the intermediate layer (I) that will make by said polyolefins foams, polyurethane foam body and thermoplastic elastic foams earlier and above-mentioned improved polyalkene based elastomers intermediate layer (II) of making and above-mentioned polymer, then this 3 synusia material adsorbed close is used on the mould intracavity wall face of metal die in vacuum forming, obtained having the standby formed products of recess;

Then make this standby formed products be close to above-mentioned vacuum forming with the state on the metal die mould intracavity wall face under or be close to matched moulds under the state on the forming metal mould mould intracavity wall face that separates with metal die with above-mentioned vacuum forming, obtain having the formed products of recess;

The synthetic resin injection that will be in the plasticization state that flows again is close to the formed products recess internal shaping on the above-mentioned metal die mould intracavity wall face and obtains 1 lamination formed body of being put down in writing of claim the.

The 2nd kind of lamination molded article production method among the present invention is characterised in that, through following operation, the i.e. 3 synusia material preheatings that constitute of the epidermal area made of the intermediate layer (I) that will make by said polyolefins foams, polyurethane foam body and thermoplastic elastic foams earlier and above-mentioned improved polyalkene based elastomers intermediate layer (II) of making and above-mentioned polymer, then this 3 synusia material adsorbed close is used on the mould intracavity wall face of metal die in vacuum forming, obtained having the standby formed products of recess;

The synthetic resin that will be in the plasticization state that flows then injects and is close to above-mentioned vacuum forming with in the standby formed products recess on the metal die mould intracavity wall face, or inject in the recess be close to the standby formed products on the forming metal mould mould intracavity wall face that above-mentioned vacuum forming separates with metal die and carry out drawing, thereby obtain 1 lamination formed body of being put down in writing of claim the.

The manufacture method of the 3rd kind of lamination formed body is characterised in that among the present invention, the 4 synusia material preheatings that the top layer that intermediate layer (II) that intermediate layer (I) that the central core that will be made by above-mentioned synthetic resin and said polyolefins foams, polyurethane foam body and thermoplastic elastic foams are made and above-mentioned improved polyalkene based elastomers are made and above-mentioned polymer are made constitutes, then with this 4 synusia material vacuum forming, and obtain 1 lamination formed body of being put down in writing of claim the.

The characteristics of the 2nd kind of lamination formed body are among the present invention, the sandwich layer made from synthetic resin by (first) and (second) by place on this sandwich layer, through at least a kind of grafted monomers selecting from the colony that the derivative of unsaturated carboxylic acid, unsaturated carboxylic acid, unsaturated epoxy monomer and unsaturated carboxylic monomer form and the top layer formation that the intermediate layer (II) that the improved polyalkene based elastomers of graft modification is made and (third) place at least a kind of polymer on this intermediate layer (II), that select from the colony that polyamide, polyurethane and polyester form to make.

The 4th kind of lamination molded article production method is characterised in that among the present invention, 2 synusia material preheatings of the top layer formation that the intermediate layer (II) that promptly will be made by above-mentioned improved polyalkene based elastomers earlier through following operation and above-mentioned polymer are made, then with this 2 synusia material adsorbed close in vacuum forming with on the mould intracavity wall face of metal die, obtain having the operation of the standby formed products of recess;

Then make this standby formed products be close to above-mentioned vacuum forming with the state on the metal die mould intracavity wall face under or be close to matched moulds under the state on the forming metal mould mould intracavity wall face that separates with metal die with above-mentioned vacuum forming, obtain having the formed products of recess;

The synthetic resin that will be in the plasticization state that flows again injects in the formed products recess that is close on the above-mentioned metal die mould intracavity wall face and is shaped, so obtain 5 lamination formed bodies of being put down in writing of claim the.

The 5th kind of lamination molded article production method is characterised in that among the present invention, the 2 synusia material preheatings that the top layer constituted that the intermediate layer (II) that promptly will be made by above-mentioned improved polyalkene based elastomers earlier through following operation and above-mentioned polymer are made, then this 2 synusia material adsorbed close is used on the mould intracavity wall face of metal die in vacuum forming, obtained having the standby formed products of recess;

The synthetic resin that will be in the plasticization state that flows then inject be close to above-mentioned vacuum forming with in the standby formed products recess on the metal die mould intracavity wall face or injection be close in the recess of the standby formed products on the forming metal mould mould intracavity wall face that separates with metal die with above-mentioned vacuum forming and drawing, thereby obtain the lamination formed body of 5 records of claim the.

The characteristics of the 6th kind of lamination molded article production method are among the present invention, the 3 synusia material preheatings that constitute of the sandwich layer that will make by above-mentioned synthetic resin and above-mentioned improved polyalkene based elastomers intermediate layer (II) of making and the above-mentioned polymer top layer of making earlier, then with this 3 synusia material vacuum forming, and obtain 5 lamination formed bodies of being put down in writing of claim the.

In addition, in first and second lamination formed body of the present invention, be located at the top layer of selecting in the group on the intermediate layer (II), that form by polyamide, polyurethane and polyester that at least a polymer constituted and also can fluff and band.

In addition, " sheet material " speech that uses in the present disclosure also has the connotation of film.

Fig. 1 (a)-(b) is the artwork of the 1st kind and the 4th kind lamination molded article production method among relevant the present invention, and Fig. 2 is a sketch that installs used in the relevant manufacture method of lamination formed body of the present invention, and Fig. 3 is the plane at expression sampling position.

Below, specifically describe lamination formed body and manufacture method thereof among the present invention according to drawing.

The 1st kind of lamination formed body among the present invention is described earlier.

The 1st kind of lamination formed body among the present invention is the top layer that the sandwich layer made by synthetic resin and polyolefin foam, polyurethane foam body and the thermoplastic elastic foams intermediate layer (I) of making and the improved polyalkene based elastomers intermediate layer (II) of making and specific polymer are made Consist of.

Sandwich layer

Sandwich layer among the present invention is made by synthetic resin. In the present invention, be to use the synthetic resin such as thermoplastic resin, thermoplastic elastomer (TPE) preferably.

As above-mentioned thermoplastic resin, specifically, do not consider crystallinity and amorphism, can enumerate low density polyethylene (LDPE), high density polyethylene (HDPE), polypropylene, poly 1-butene, poly(4-methyl-1-pentene), or ethene, propylene, the 1-butylene, the polyolefin of the random or block copolymer of the alpha-olefines of 4-methyl-1-pentene etc. etc., ethylene acrylic acid co polymer, ethylene vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, the ethylene-vinyl compound copolymers such as ethene vinyl chloride copolymer, polystyrene, acrylonitrile styrene copolymer, ABS, styrene-methyl methacrylate copolymer, the phenylethylene resin series such as AMS styrol copolymer, polyvinyl chloride, polyvinylidene chloride, the vinyl chloride vinylidene chloride copolymer, PMA, the polyvinyls such as polymethyl methyl esters, nylon 6, nylon 6-6, nylon 6-10, nylon 11, nylon 12 polyamide such as grade, PET, the thermoplastic polyesters such as polybutene terephalic acid ester, Merlon, polyphenylene oxide compound etc. or their mixture, or silicone-based, the resins such as urethanes system.

As above-mentioned thermoplastic elastomer (TPE), specifically, can enumerate and consist of the back with the improved polyalkene based elastomers in the intermediate layer (II) of narration, polyolefin elastomer, styrene series elastomer, ester based elastomers, urethanes based elastomers, vinyl chloride elastomer etc.

In the present invention, consider the factors such as molding condition, purposes, character, price, from above-mentioned various synthetic resin, select suitable synthetic resin. But from aspects such as the resistance to impact of resulting lamination formed body, against weathers, polyolefin-based resins, particularly polyacrylic use are more welcome.

Also have, the present invention can as required, make above-mentioned synthetic resin foaming with blowing agent, or for further improving performance, in the scope of desired performance, can add the additives such as wood chip, fibre plate, inorganic filler in above-mentioned synthetic resin.

Intermediate layer (I)

Intermediate layer among the present invention (I) is made by polyolefin foam, polyurethane foam body or thermoplastic elastic foams.

As the said polyolefins foams, specifically, can enumerate polyethylene foam, the foams of polypropylene foam, polyethylene and polypropylene miser etc.

When above-mentioned polyurethane foam body is used for intermediate layer (I), from flexibility, heat resistance and sound absorption properties equal angles, it is more satisfactory using with the flexible foam body of subcontinuous foaming structure and the polyurethane foam body of scope about about 10-100 times of expansion ratio.

Consisting of the thermoplastic elastomer (TPE) of thermoplastic elastic foams used among the present invention, is olefin series thermoplastic elastomer, for example, and with polyolefin-based resins and the ethylene ' alpha '-olefin based copolymer rubber thermoplastic elastomer (TPE) as essential component.

In the present invention, above-mentioned ethylene ' alpha '-olefin based copolymer rubber if use the partial cross-linked thing of ethylene ' alpha '-olefin based copolymer rubber then to imitate as effect, but also can use the non-crosslinked thing of ethylene ' alpha '-olefin based copolymer rubber.

As the thermoplastic elastomer (TPE) preferably of result of use in the present invention, specifically, can enumerate following thermoplastic resin composition.

(I) with the homopolymers of ethene or propylene or and the bipolymer rubber that forms of the various polyolefin-based resins of the copolymer representative that forms of other a small amount of polymerizable monomers and α-polyolefin by ethene and carbon 3-14 or the partial cross-linked phase of the copolymer rubber ethylene-alpha of itself and the formed ternary of the further copolymerization of various polyenic compounds and even quaternary-polyolefin copolymer rubber mixed and the thermoplastic resin composition that obtains, (such as reference examined patent publication 53-21021 number and JP 55-71738 communique).

The mixture that (II) forms polyolefin-based resins and ethylene ' alpha '-olefin based copolymer rubber carries out the thermoplastic resin composition that Dynamic heat-treatment obtains (such as examined patent publication 53-34210 number, JP 53-149240 communique and JP 53-149241 communique) in the presence of a small amount of crosslinking agent.

(III) mixes the constituent of above-mentioned (I) or (II) and the thermoplastic resin composition (opening clear 53-145857 communique and the clear 54-16554 communique of Te Kai as the spy) that obtains again with polyolefin-based resins.

(IV) with the homopolymers of ethene or and the homopolymers of the peroxide thing cross-linking type polyolefin-based resins of the copolymer representative that forms of a spot of other polymerizable monomers, propylene or and the peroxide thing non-crosslinked type polyolefin-based resins of the copolymer representative that forms of a spot of other polymerizable monomers, and the mixture of ethylene ' alpha '-olefin based copolymer rubber is in the presence of a small amount of peroxide thing, carries out the thermoplastic resin composition (opening clear 55, No. 71739 communiques as the spy) that obtains after the dynamic heat treatment etc.

In above-mentioned various thermoplastic elastomer (TPE)s, polyolefin-based resins and ethylene ' alpha '-olefin based polymer rubber weight ratio in use are generally 90/10-10/90, are preferably 80/20-20/80.

To polyolefin-based resins,, polyethylene, particularly low density polyethylene (LDPE) and polypropylene can be used after mixing by the weight ratio of 10/90-70/30 for the traumatic resistance that improves formability, sheet material etc.

To ethylene ' alpha '-olefin based polymer rubber, mainly due to the reason of intensity aspect, the ideal range of the mol ratio of ethene and alpha-olefin is 50/50-90/10, is preferably in 70/30-85/15, in addition, wishes to use Mooney viscosity ML ₁₊₄(121 ℃) are preferably in the ethylene ' alpha '-olefin based polymer rubber of about 40-80 about more than 20.These ethylene ' alpha '-olefin based polymer rubber parts when crosslinked, are generally said, preferably thermoplastic elastomer (TPE) 100 weight are used the organic peroxy thing of about 0.1-2 weight, carry out dynamic heat treatment then.

Thermoplastic elastomer (TPE) among the present invention, also can contain in above-mentioned thermoplastic resin composition as required with polyisobutene, buttress rubber is that the peroxide thing non-crosslinked type hydrocarbon system rubber-like substance and/or the oil of representative is soft dose.

Used thermoplastic elastic foams among the present invention normally obtain the not foam sheet of above-mentioned thermoplastic elastomer (TPE) after heating.

Constitute the thermoplastic elastomer (TPE) of the not foam sheet of above-mentioned thermoplastic elastomer (TPE), remove and contain the external blowing agent that also contains as essential composition of above-mentioned thermoplastic elastic.

As blowing agent used among the present invention, specifically, can enumerate the inorganic foaming agent of sodium acid carbonate, sodium carbonate, carbonic hydroammonium, ammonium carbonate, ammonium nilrite etc.; N, N '-dimethyl-N, N '-two nitrous acid terephthaloyl amine, N, the nitrous compound of N '-two nitrous acid pentamethylene pentamethylene tetramine etc.; Azo-compound, benzene sulfonyl hydrazide, toluene sulfonyl hydrazide, the P of azodicarboxy acid amides, azodiisobutyronitrile, azo cyclohexanenitrile, azo diaminobenzene, barium azo-dicarboxylic salt etc., P '-oxo two (benzene sulfonyl hydrazide), two benzene sulfonyls-3,3 '-sulfohydrazide compounds such as disulfonyl hydrazide; Nitrine calcium, 4,4 '-nitrine diphenyl disulfonyl, nitrine be to the azide of benzene methylsulfonyl etc.Wherein, the nitrine formamide is more desirable.

In the present invention, the ratio of contained blowing agent is 0.1-50 weight % in the not foam sheet of thermoplastic elastomer, is preferably 0.5-20 weight %.

In the present invention, the not foam sheet of above-mentioned thermoplastic elastomer normally adopts forming process, stack forming process etc. to form.

The thickness of the not foam sheet of employed thermoplastic elastomer (TPE) is generally 0.05-5.0mm among the present invention, is preferably 0.1-3.0mm.

Then, the not foam sheet of above-mentioned thermoplastic elastomer (TPE) heated make it foaming, so obtain the foaming body of thermoplastic elastomer (TPE).This heating is preferably in the air-oven to be carried out, but also can adopt other heating means.

The condition of above-mentioned heating normally, temperature is 160-260 ℃, is preferably 170-250 ℃ that be the 0.5-10 branch heat time heating time, is preferably 2-5 minute.

In the present invention, the multiplying power of above-mentioned foaming, normally 1.1-20 doubly it would be desirable that 1.2-5 is doubly.The thickness of foaming layer, normally 0.1-10mm it would be desirable 0.2-5mm.

As above-mentioned thermoplastic elastic foams are used for the intermediate layer, can obtain shape and knuckle line is clear, and have the lamination formed body of good soft feeling.

Intermediate layer (II)

As follows as can specifically exemplifying of the improved polyalkene based elastomers that constitutes intermediate layer (II) used among the present invention:

To contain (a) peroxide thing cross-linking type olefin copolymer rubber 100-10 weight portion, it is desirable to the 95-10 weight portion, preferably 95-60 weight portion and (b) olefin series plastic 0-90 weight portion, it is desirable to the 5-90 weight portion, preferably the 5-40 weight portion [(a) composition and (b) the total amount of composition be 100 weight portions] with (c) from unsaturated carboxylic acid, the derivative of unsaturated carboxylic acid, at least a kind of grafted monomers 0.01-10 weight portion selecting in unsaturated epoxy monomer and the formed group of unsaturated hydroxyl monomer, it is desirable to the mixture of 0.1-5 weight portion, in the presence of organic peroxy thing, carry out dynamic heat treatment, make its partial cross-linked and thermoplastic elastomer (TPE) of obtaining etc. usually.

In addition, the mixture that need are heat-treated, can except that above-mentioned (a)-(c) composition, allocate composition (a) and (b) (the total amount is about 100 weight portions), (d) peroxide thing non-crosslinked type rubber-like substance 0-100 weight portion again into, it is desirable to the 5-100 weight portion, preferably the 5-50 weight portion and (or) (e) petroleum line softener 0-200 weight portion, it is desirable to 3-100 weight portion, 3-80 weight portion preferably, to improve the shaping processability of resulting thermoplastic elastomer (TPE).

By composition (a) being cooperated, can make the constituent that obtains when having good rubber properties such as caoutchouc elasticity, has good formability in above-mentioned scope.

By in above-mentioned scope, cooperating with composition (b), (d) with (e), can make the constituent that obtains when having good rubber rerum naturas such as caoutchouc elasticity, have good flowability and formability.

By composition (c) is cooperated in above-mentioned scope, can make the composition that obtains have good formability and to the good thermal bonding of resin and metal.

(a) peroxide thing cross-linking type olefin copolymer rubber

Employed peroxide thing cross-linking type olefin copolymer rubber among the present invention, be meant ethylene-propylene copolymer rubber, ethylene-propylene non-conjugated diene hydrocarbon rubbers, such the mixing of ethylene-butadiene copolymer rubber with the amorphous elastomeric copolymer and the organic peroxy thing of alkene as main component, make it crosslinked by mixing under heating, become mobile little or immobilising rubber.Also have, the non-conjugated diene hydrocarbon is meant dicyclopentadiene, 1,4-hexadiene, homotropilidene, methylene ENB, inferior second ENB etc.

In the present invention, the ethylene-propylene copolymer rubber in these copolymer rubbers, ethylene-propylene non-conjugated diene hydrocarbon rubbers result of use are better.Usually use ethylene-propylene copolymer rubber, the ethylene-propylene non-conjugated diene hydrocarbon rubbers of the mol ratio (ethylene/propene) of ethene unit and propylene unit as 50/50-90/10, the ethylene-propylene copolymer rubber that particularly above-mentioned mol ratio is 55/45-85/15, ethene-olefin/unconjugated dience rubber are that result of use is better.Wherein, the inferior second of ethylene-propylene non-conjugated diene hydrocarbon copolymer rubber, particularly ethylene-propylene-5--2-norbornene copolymer rubber and the inferior second of ethylene-propylene-5--2-ENB-dicyclopentadiene quadripolymer can be made into have good hear resistance, draftability and elastic thermoplastic elastomer composition, thereby be comparatively ideal.

Mooney viscosity [the ML of above-mentioned copolymer rubber ₁₊₄(100 ℃)] more satisfactory during at 10-250, particularly at 40-150.Use the above-mentioned copolymer rubber of Mooney viscosity in this scope, can obtain having good draftability and mobile thermoplastic elastomer composition.

The iodine number of above-mentioned copolymer rubber (degree of unsaturation) be lower than 25 o'clock more satisfactory.Use the above-mentioned copolymer rubber of iodine number in this scope, can obtain thermoplastic elastomer composition mobile and that the rubber property maintenance is well balanced.

(b) olefin series plastic

Used olefin series plastic among the present invention is made up of the crystalline polymer amount solid product that obtains after adopting high-pressure process or low-pressure process with the monoolefine polymerization more than a kind or 2 kinds.This olefin series plastic can exemplify homogeneity or the copolymer resin formed as by isotactic and syndiotactic monoolefine, and their representative goodss can have been bought on market.

As proper raw material alkene, specifiable have ethene, propylene, 1-butylene, 1-amylene, 1-hexene, 2-methyl isophthalic acid-propylene, 3-Methyl-1-pentene, 4-methyl-1-pentene, 5-methyl isophthalic acid-hexene, 1-octene, 1-decene and their the mixed stocker alkene more than 2 kinds.The mode of polymerization, no matter be random or become the piece type, as long as can obtain resinoid, all can adopt.

Wherein, comparatively ideal olefin series plastic is peroxide thing breakdown type olefin series plastic and polyethylene.

Peroxide thing breakdown type olefin series plastic is meant by mixing with the peroxide thing and heating is mixed, and makes it carry out thermal decomposition, to reduce molecular weight, improves the olefin series plastic of Resin Flow.Can be used as that this olefin series plastic enumerates, the copolymer that isotactic polypropylene or propylene and other a spot of alpha-olefins are arranged is as propylene-ethylene copolymers, propylene-butene-1 copolymer, propylene-1-hexene copolymer, propylene-4 methyl 1 pentene copolymer etc.The ideal range of the melt index of the olefin series plastic that in above-mentioned mixing, uses (A STM-D-1238-85T, 230 ℃) as 0.1-50, be preferably 5-20.In the present invention, olefin series plastic helps to improve the flowability and the hear resistance of constituent.

(c) unsaturated carboxylic acid or derivatives thereof, unsaturated epoxy monomer, unsaturated hydroxyl monomer

The unsaturated carboxylic acid or derivatives thereof that uses as one of (c) composition among the present invention, the concrete specifiable acrylic acid that has, methacrylate, maleic acid, fumaric acid, itaconic acid, pyrocitric acid, the α of tetrahydrochysene phthalandione etc., beta-unsaturated carboxylic acid, two rings [2,2,1] hept-2-ene"-5, the unsaturated carboxylic acid of 6-dicarboxylic acids etc., anhydrous maleic acid, anhydrous itaconic acid, anhydrous pyrocitric acid, the α of tetrahydrochysene anhydrous phthalic acid etc., the anhydride of β unsaturated carboxylic acid, two rings [2,2,1] hept-2-ene"-5, the anhydride of the unsaturated carboxylic acid of 6-dicarboxylic acids anhydride etc., methyl acrylate, methylmethacrylate, the maleic acid dimethyl, the maleic acid monomethyl, the fumaric acid dimethyl, the itaconic acid dimethyl, the pyrocitric acid dimethyl, tetrahydrochysene anhydrous phthalic acid dimethyl, two rings [2,2,1] hept-2-ene"-5, the ester of unsaturated carboxylic acids such as 6-dicarboxylic acids dimethyl etc.Wherein, maleic acid, two ring [2,2,1] hept-2-ene"s-5,6-dicarboxylic acids or their anhydride use more.

Unsaturated epoxy monomer as (c) composition another part among the present invention, specifically, be preferably epihydric alcohol acrylic ester, epihydric alcohol methylpropenoic acid ester, the ethylene oxidic ester of the unsaturated monocarboxylic acid of p-styrene carboxylic acid ethylene oxidic ester etc., maleic acid, itaconic acid, pyrocitric acid, the butylene tricarboxylic acids, internally-oriented cis two rings [2,2,1] heptan-5-alkene-2, the 3-dicarboxylic acids, internally-oriented cis two rings [2,2,1] heptan-5-alkene-2-methyl-2, unsaturated polycarboxylic glycidol one acid esters or the glycidol polyacid ester of 3-dicarboxylic acids etc.: glycidol allyl propionate, 2-glycidol acid methyl allyl ester, the glycidic ester of neighbour-chavicol, between-glycidic ester of chavicol, the glycidic ester of right-chavicol, the glycidic ester of isopropenyl phenol, the glycidic ester of neighbour-vinylphenol, between-glycidic ester of vinylphenol, the unsaturated glycidic ester of the glycidic ester of right-vinylphenol etc.: 2-(neighbour-ethenylphenyl) oxireme, 2-(is right-ethenylphenyl) and oxireme, 2-(neighbour-ethenylphenyl) propylene oxide, 2-(is right-ethenylphenyl) and expoxy propane, 2-(neighbour-allyl phenyl) oxirane, 2-(is right-allyl phenyl) and oxirane, 2-(o-allyl base) expoxy propane, 2-(is right-allyl phenyl) and expoxy propane, right-glycidol styrene, 8,4-epoxy-1-butylene, 3,4-epoxy-3-methyl-1-butene, 8,4-epoxy-1-amylene, 3,4-epoxy-3-Methyl-1-pentene, 5,6-epoxy-1-hexene, one oxyethylene group cyclohexene, pi-allyl-2,3-epoxide ring amyl ether etc.

Unsaturated carboxylic monomer as another part of (c) composition among the present invention is the monomer with each more than one ethene unsaturated bond and hydroxyl, concrete specifiable have hydroxy ethyl methacrylate, hydroxypropyl acrylate, hydroxyethyl meth acrylate, hydroxypropyl methyl acrylate, polyethylene glycol (-) methacrylate, polypropylene glycol (-) methacrylate etc., good especially is hydroxyalkyl vinyl () acrylate and hydroxypropyl () acrylate.

Above-mentioned (c) composition, when carrying out the dynamic heat treatment that to narrate the back, work as the graft modification agent, can strengthen the top layer that constitutes by polyamide, polyurethane or polyester and the intermediate layer (II) that constitutes by the improved polyalkene based elastomers between the bonding force at lamination interface.

(d) peroxide thing non-crosslinked type rubber-like substance

Above-mentioned (d) composition peroxide thing non-crosslinked type rubber-like substance, be meant as the propylene-ethylene copolymers rubber more than polyisobutene, buttress rubber (I I R), 70 moles of % of propylene, random polypropylene etc., even they are to mix, heat and mix with the peroxide thing, can crosslinked, can not reduce mobile hydrocarbon system rubber-like substance yet.Wherein the performance and the behaviour in service of polyisobutene and buttress rubber (I I R) are optimal.

It is optimum at the peroxide thing non-crosslinked type rubber-like substance below 60 that peroxide thing non-crosslinked type rubber-like substance can improve the flowability, particularly Mooney viscosity of thermoplastic elastomer composition.

(e) petroleum line softener

Above-mentioned (e) composition petroleum line softener, normally high boiling petroleum distillate, can be divided into paraffin series, naphthene series and fragrant family, its effect is with Roller Machining rubber the time, weakening the active force between rubber molecule, when being convenient to process, also can help dispersions such as the carbon black allocated into as filler and cabosil, or be used for reducing the hardness of vulcanized rubber, to increase flexibility and elasticity.

The production of improved polyalkene based elastomers

In lamination formed body of the present invention, constitute the improved polyalkene based elastomers in intermediate layer (II), be with above-mentioned (a) to the various compositions of (c) and as required, add (d) and/or various compositions (e) mix by foregoing amount ratio, under the condition that organic peroxide exists, carry out dynamic heat treatment, produce by making its partial cross-linked method.

In addition, not undermining improved polyalkene is the elastomeric flowability of thermoplasticity (formability), the character in rubber school, and by polyamide, in the scope of the adhesive property on the top layer that polyurethane kind or polyester are formed, can allocate the filler of condensating fiber shape into, polyolefin plastics, perhaps filler, for example, glass fibre, potassium titanate fibre, high density polyethylene (HDPE), medium density polyethylene, low density polyethylene (LDPE), isotactic polypropylene, propylene-α-polyolefin copolymers, calcium carbonate, calcium silicates, clay, potter's clay, talcum, silica, diatomite, mica powder, pitch, alumina, barium sulfate, aluminum sulfate, calcium sulfate, basic magnesium carbonate, molybdenum bisuphide, graphite, glass fibre, glass marble, carbon fibre etc., perhaps colouring agent, for example carbon black, titanium oxide, zinc oxide, iron oxide, ultramarine, dark purple, AZOpigments, nitroso pigments, lake, phthalocyanine dye or the like.

In addition, in the present invention, also can be with phenol, sulfurous acid system, benzene chain methane series, phosphatization system, perhaps be lubrication prescription of well-known heat-resisting stabilizing agent, age resister, weatherability stabilizing agent, charged preventor, metallic soaps, paraffin etc. such as stabilizing agent etc., press olefin series plastic or the employed amount of olefin-based EVA rubber proportioning in addition as ammonia.

In the present invention, be to exist under the condition of organic peroxide, above-mentioned various mixture of ingredients are carried out dynamic heat treatment, make it partial cross-linked, thereby make the improved polyalkene based elastomers.

So-called dynamic heat treatment refers in the mixing of melting under the state.

In the present invention, used organic peroxide when producing the improved polyalkene based elastomers, get on very well particularly, can lift cumyl peroxide, two-tert-butyl peroxide, 2,5-dimethyl-2,5-two (tert-butyl peroxide) hexane, 2,5-dimethyl-2,5-two (tert-butyl peroxide) hexin-3,1,3-two (tert-butyl peroxide isopropyl) benzene, 1,1-two (tert-butyl peroxide)-3,3, the 5-trimethyl-cyclohexane, just-butyl-4,4-two (tert-butyl peroxide) バ レ レ-ト, the benzoyl peroxide, right-chlorobenzene acyl peroxide, 2,4-dichloro benzoyl peroxide, tert-butyl peroxide benzoate fiber, right-butyl benzylhydroperoxide fat fiber, tert-butyl peroxide isopropyl carbonate, the diacetyl peroxide, the dodecanoyl peroxide, tert-butyl cuminyl peroxide or the like.

Wherein, aspect foul smell, coking stable, comparatively it is desirable to 2,5-dimethyl-2,5-two (tert-butyl peroxide) hexane, 2,5-dimethyl-2,5-two (tert-butyl peroxide) hexin-3,1,3-two (tert-butyl peroxide isopropyl) benzene, 1,1-two (tert-butyl peroxide)-3,3,5-trimethyl-cyclohexane and just-butyl-4,4-two (tert-butyl peroxide) バ レ レ-ト or the like, wherein, especially with 1, (tert-butyl peroxide cumene is ideal for 3-two.The proportional quantity of this organic peroxide should be chosen in the above-mentioned (a) and (b) and (c) the 0.05-3 weight % of the total weight of composition, preferably in the scope of 0.1-1 weight %.If can be controlled at their proportional quantity in the above-mentioned scope, rubber properties of the hear resistance of resulting improved polyalkene based elastomers, tensile properties, elasticity recovery and backwash elasticity or the like and intensity are very good, and its forming property is also very desirable.

The content of (c) composition in the improved polyalkene based elastomers constituent can be measured with infrared absorbency analytic approach or chemical analysis.

Mixed stirring device specifically, usefulness be that opening stirring is rolled or well-known in the past mixed stirring devices such as the Banbury mixer of non-style of opening, extruder, kneading machine, continuous mixer.Wherein, preferably select to use the device of non-style of opening.In addition, when mixing, preferably in the environment of inert gases such as nitrogen, carbonic acid gas, carry out.When mix stirring, should be with half-life of employed organic peroxide temperature less than 1 minute, generally be 150-280 ℃, preferably 170-240 ℃ temperature, carried out preferably 1-10 minute 1-20 minute.In addition, the shearing force of adding up with shear rate, generally is 10-10 ⁴Sec ^-1, comparatively it is desirable to 10 ²-10 ⁸Sce ^-1

In the present invention, when carrying out partial cross-linked processing with above-mentioned organic peroxide, can cooperate as Sulfur, p-benzoquinones two oximidos, p, p-DBQD base, N-methyl-N, the 4-dinitrosoaniline, nitrosobenzene, the diphenylamines guanidine, trimethylolpropane-N, peroxyde crosslinked auxiliary agents such as N-m-benzene two maleimides, perhaps as divinylbenzene, the triallyl melamine, erethin ethyleneglycol dimethacrylate salt, divinyl ethyleneglycol dimethacrylate salt, the polyethylene glycol dimethacrylate, the trimethylol propane trimethyl acrylates, how dynamopathic methacrylic acid salt monomers such as acrylic methacrylate, hylene butyric acid salt or as multimachines such as ethene stearate can sex ethylene monomer.By such compound, just can obtain evenly and the cross-linking reaction that relaxes.Especially in the present invention, as used divinylbenzene, then deal with very convenient, with with above-mentioned substance to be processed be the intermiscibility of the olefin-based rubber of main component and olefin series plastic for very good, and have the liquefiable effect of organic peroxide, can play the effect of snperoxiaized dispersing aid, so, very even by the cross-linking effect that heat treatment is carried out, can obtain the component that flowing property and physical property balance each other, so be the best approach.In the present invention, the combined amount of this crosslinking coagent or multimachine energy sex ethylene monomer should be chosen in to substance to be processed in general, be 0.1-2 weight %, preferably should be in the scope of 0.3-1 weight %, by mixing in this scope, it is good and can not bring component component because of the variation of the caused physical property of thermo-lag when shaping to access mobile performance.

In addition,, also can use triethylamine, tri-butylamine, 2,4, the decomposition accelerating agent of naphthenic acid salt of tertiary amine such as 6-three (dimethyl amine) phenol or aluminium, cobalt, barium, copper, calcium, zirconium, manganese, lead, mercury etc. etc. in order to promote the decomposition of organic peroxide.

By dynamic heat treatment aforesaid, under the organic peroxide existence condition, just can carry out the crosslinked of part, simultaneously,, just can obtain the polyolefin elastomer of graft modification by the composition of above-mentioned (c).

In addition, in the present invention, so-called graft modification olefin-based elastomer is meant by partial cross-linked, and the content of the gelinite of measuring with following method is in more than 20%, it is desirable in the scope of 20-99.5%, and be the best with the scope of 45-98% especially wherein.

The gelinite Determination on content:

Get 100mg thermoplastic elastomer (TPE) sample with balance, it is cut into the shred of 0.5mm * 0.5mm * 0.5mm, this shred is put into a sealed container, under the condition of 23 ℃ of temperature, dipping took out sample after 48 hours in the cyclohexane of 30ml, be placed on the filter paper, at ambient temperature, place more than 72 hours, be dried to till the constant always.

After this drying the weight of residue, deduct the weight of component of polymer all cyclohexane insoluble compositions (bat wool, filler, pigment) in addition and the weight of the olefin series plastic composition in the preceding sample of cyclohexane dipping, resulting being " revised final weight (Y) ".

In addition, the weight of the peroxide crosslinking type olefin copolymer rubber in the sample, (for example promptly from the weight of sample, deduct (1) peroxide crosslinking type olefin copolymer rubber cyclohexane soluble component in addition, Dormant oils and plasticiser) and (2) olefin series plastic composition, (3) condensate composition beyond the value of weight of cyclohexane insoluble composition (bat wool, filler, pigment etc.) after, can be used as " revised initial stage weight (x) ".

At this, the content of gelinite, available following formula is tried to achieve.

Gelinite content (weight %)=(revised final weight (Y))/(revised initial stage weight (X)) * 100

Above-mentioned sex change polyolefin elastomer has good flexibility, hear resistance and cold resistance, and all very good with the adhesive property of polyamide, polyurethane and polyester.

The top layer

Constituting the polymer on top layer used in the present invention, is the selected at least a polymer that comes out from colony's material that polyamide, polyurethane and polyester are formed.

The used polyamide of the present invention has hexamethylene diamine, ten methene diamines, 12 methene diamines, 2,2,4 or 2,4,4 trimethyl oxygen methene diamines, 1,3 or 1,4-two (amine methyl) cyclohexane, two (right-aminocyclohexane methane), between-or the aliphatic of right-benzene two methanediamines etc., alicyclic, the adipic acid of aromatic series etc., suberic acid, aliphatic acid, cyclohexane dicarboxylic acid, terephthalic acids, the aliphatic of different isophthalic acid etc., alicyclic, aromatic series etc. and the resulting polyamide of polycondensation dicarboxylic acids, ε-lpsilon, the resulting polyamide of condensation through amino carboxylic acid of 11-aminoundecanoic acid etc., from ε-own lactones, resulting polyamide or by these copolymer polyamide that becomes branch to form in the ester of ω-ten diester etc., mixture of these polyamide or the like.Get on very well particularly, nylon 6, nylon 66, NYLON610, nylon 9, nylon 11, nylon 12, nylon 6166, nylon 661610, nylon 6/11 or the like are arranged.

Used polyurethane among the present invention, available all known polyurethane kinds at present, for example, the polyurethane of the polyester system of classifying or the polyurethane of polyethers system and soft, the semi-hard or rigid polyurethane of classifying or the like from the hardness aspect from raw polyol composition aspect, in a word, any polyurethane all can use.

Especially when lamination formed body of the present invention being used for the vehicle inner decoration material of automobile etc., it is comparatively desirable to form the top layer with the form of polyurethane sheet material.At this moment, for this point of easy lamination, preferably use thermoplastic polyurethane.

Used polyester among the present invention specifically, has thermoplastic polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene isophthalic acid salt.

Above-mentioned polyamide, polyurethane, polyester all have good hear resistance, oil resistivity, solvent resistance, abrasion resistance and traumatic resistance, so the most suitable cladding material of doing the formed body surface of their polymer.

Also can fluff and band in above-mentioned this top layer, have the laminated body that the top layer is banded in fluffing, has more good soft feeling and good hand feeling, and simultaneously, its oil resistivity, solvent resistance, abrasion resistance etc. are also very desirable.

The method that is fluffed in the top layer to band, can adopt (a) to rub with sand paper, the wildness on top layer is banded, (b) by an iron wire roller, the wildness on top layer is banded, (c) with the method for polishings such as belt polishing or drum polishing make that the wildness on top layer bands, (d) thus Japan's special permission disclose put down in writing on clear and 62-275, No. 732 communiques allow hot fine particle impact up to make method that the top layer wildness bands etc., and method is banded in well-known in the past fluffing.

Top introduce by sandwich layer/intermediate layer (I)/intermediate layer (II)/4 layers of the 1st lamination formed body of the present invention of being formed such as top layer, can make with the of the present invention the 1st, the 2nd or the 3rd kind of manufacture method of following introduction.

At first introduce the manufacture method of the 1st lamination formed body among the present invention.

The 1st procedure in the 1st manufacture method that the present invention introduces, be after preheating by above-mentioned intermediate layer (I), above-mentioned intermediate layer (II), the above-mentioned 3 synusia materials of being formed by polyolefin foam, polyurethane foaming body, thermoplasticity elastic foam of being formed by the improved polyalkene based elastomers of forming by condensate that the top layer constituted, this three-layer tablet material is attracted to be close to vacuum forming with on the mould intracavity wall of metal pattern, just can obtain having the preformed articles of recess.

The manufacture method of 3 above-mentioned synusia materials, shape according to final products, size, the difference of desired physical property etc. and different, but generally speaking, manufacture method as above-mentioned 3 synusia materials, have for example by above-mentioned polyolefin foam, the sheet material that polyurethane foaming body or thermoplastic elastomer foaming body are formed, sheet material of being formed by above-mentioned improved polyalkene based elastomers and the sheet material of forming by above-mentioned condensate, use the calender roll forming machine, forming machines such as compressing forming machine, after heat merges, the manufacture method of the 3 synusia materials that just can obtain introducing above.

In addition, in the present invention, also can use the embossing roller as required, on the surface on the above-mentioned top layer of forming by polymer, carry out embossing processing, also can be in printing process, at the surface printing literal on top layer, pattern, style or the like.

In the present invention, though the thickness of 3 each layers of synusia material is different because of the difference of lamination formed body purposes, but in general, the THICKNESS CONTROL of intermediate layer (I) is comparatively desirable in the scope of 5-500 μ m in the THICKNESS CONTROL on 0.1-50mm, top layer in the THICKNESS CONTROL of 0.5-10mm, intermediate layer (II).

In the manufacture method of the 1st lamination formed body of mentioning among the present invention, can use the sort of device as shown in Figure 1.Such as Fig. 1 (a)-(d) shown in of this device has a pair of vacuum-formed injection model metal mould for formation (1,2) that carries out of negative and positive at least.And owing on former 1,, attract passage 7 and be formed with the air that is connected with vavuum pump 6 in order to make negative pressureization in the die cavity 3.In addition, on the mould intracavity wall face of former 1, carve as required and established decorative pattern or stripe.

Under the state that this negative and positive pair of metal mould (1,2) is opened, unfold 3 above-mentioned synusia materials 4, make it peristome [Fig. 1 (a)] as the die cavity that covers former 1, preheating is carried out near this peristome 3 synusia materials 4 partly in the heating part 5 of preheating apparatus.Preheat temperature is generally 150-200 ℃.Except with the approaching method in above-mentioned heating part 5, can also select blowing hot-air, contact warm-up mill or the like the whole bag of tricks as the preheating means.

After this, attract, make negative pressureization in former 1 die cavity 3, allow 3 above-mentioned synusia materials 4 attract to abut against on the internal face of this die cavity, to obtain preform product [Fig. 1 (b)] with vavuum pump 6.

At this moment, 3 synusia materials 4 are bonding very well according to the die cavity shape of metal pattern (1,2), so can not crack or wrinkle in the local area.In addition, owing to embed to form dearly on candy strip concavo-convex, so striped can very well clearly duplicate out.

Then, it is the 2nd procedure in the 1st manufacture method introduced of the present invention, resulting preformed articles in the 1st operation, at the state of tightly being close on the above-mentioned vacuum forming usefulness mould intracavity wall face of metal pattern, perhaps tightly be close under the state of above-mentioned vacuum forming with the mould intracavity wall face of other metal mould for formation beyond the metal pattern, close up model, just can obtain having the formed products of recess.

The operation of above-mentioned matched moulds, shown in Fig. 1 (c) like that, carry out with a pair of metal pattern of negative and positive (1,2).

At last, enter the 3rd procedure in the 1st manufacture method that the present invention introduces, promptly in the recess of the formed products that is close to above-mentioned metal pattern mould intracavity wall face, inject the synthetic resin that is in the plastifying state that flows, just can be shaped.

Above-mentioned what is called is in the synthetic resin in the plastifying state that flows, and for example refers to heat, mix, disperse the resulting shape resin that dissolves in back with screw extruder, or makes its resin that becomes the plastifying state material that flows etc. with solvent.

Above-mentioned injection molding forming, be by nozzle 8 from inejction molder, in the recess of formed products, inject and fill the synthetic resin that is under the plastifying state that flows, matched moulds is finished then, cools off then or the heating of metal mould, behind resin solidification, take out product, this product is exactly the 1st lamination organizator that the present invention introduces.

In addition, for taking out the finishing that product carried out, be in matched moulds, in metal pattern (1,2), to carry out, so in operation after this, just do not need to have repaired again.

Next introduce the manufacture method of the 2nd lamination organizator among the present invention.

The 1st procedure in the 2nd manufacture method that the present invention relates to, be the intermediate layer (I) that to be formed by said polyolefins foaming body, polyurethane foaming body or by the elastomer foamed body of plasticity after, the intermediate layer (II) be made up of above-mentioned sex change polyolefin elastomer and, the 3 synusia materials be made up of the top layer that above-mentioned condensate constituted preheat, this 3 synusia material is attracted to be close to vacuum forming with on the mould intracavity wall of metal pattern, just obtained having the preformed articles of recess.

3 above-mentioned synusia materials are identical with the 3 synusia materials of being introduced in the 1st lamination formed body production method of the present invention.

Used in the 2nd kind of manufacture method of the present invention is as shown in Figure 2 the sort of manufacturing installation.

This device as shown in Figure 2, the metal pattern (1,2) that possesses a pair of shaping usefulness, make former 1 following, formpiston 2 is last, under the state that metal pattern (1,2) is opened, heating part 5 with preheating apparatus, the 3 synusia materials 4 that preheating is above-mentioned, offer simultaneously between the metal pattern (1,2), diastole is come, to cover the die cavity peristome of former 1, after this, by the attraction of vavuum pump 6,3 above-mentioned synusia materials 4 are attracted to abut against on the mould intracavity wall face of metal pattern (1,2), so just can obtain having the preformed articles of recess.This moment, also the situation with above-mentioned the present invention's the 1st manufacture method was identical, and above-mentioned 3 synusia materials 4 are all very good to the reproduction performance of the attraction close property of metal pattern die cavity 3, striped.

Then, be the second operation work in the 2nd system method among the present invention.

In being close to the recess of above-mentioned vacuum forming with the prefabricated formed products on the mould intracavity wall of metal pattern, or in being close to the recess of above-mentioned vacuum forming with the prefabrication on the mould intracavity wall face of other metal mould for formation beyond the metal pattern, injection is in the synthetic resin under the plastifying state that flows, and has carried out drawing.

The above-mentioned synthetic resin that is in the plastifying state that flows, extruding is come out from extruder 10, and injects in the recess of prefabricated formed products from injecting nozzle 11.In addition, in the present invention, preferably can make the injection nozzle 11 that the X-Y direction moves on the recess of prefabricated formed products is all, and move according to the track of prior regulated procedure, the whole recesses that allow the synthetic resin that is in the plastifying state that flows can be injected into prefabricated formed products go.

In addition, above-mentioned what is called is in the synthetic resin of mobile plastifying state, for example refers to and dissolves the shape resin with resulting after screw extruder heating, mixing, stirring, the dispersion, or use solvent, makes it become the resin of plastifying state or the like that flows.

Above-mentioned drawing is moved as matched moulds with metal pattern 2 and to be carried out.By the operation of this matched moulds, be in the synthetic resin of the plasticization state that flows, owing to flowing into, the extruding force of metal pattern (1,2) has been full of in the die cavity 3, so after this, by methods such as coolings, solidified after the formed body, just can be used as product and take out, be i.e. the 1st lamination formed body among the present invention.

In addition, also can repair in metal pattern (1,2) in matched moulds this moment, so in operation after this, just need not finishing.

Introduce the manufacture method of the 3rd lamination formed body among the present invention below.

In the manufacture method of the 3rd the lamination formed body that the present invention relates to, after the intermediate layer (I) that the sandwich layer that will be made up of above-mentioned synthetic resin and, polyolefin foam, polyurethane foaming body or thermoplastic elastomer foaming body by above-mentioned are formed and, the intermediate layer (II) be made up of above-mentioned improved polyalkene based elastomers preheat with, the 4 synusia materials that the top layer constituted be made up of above-mentioned condensate, with this 4 synusia material vacuum forming.

The manufacture method of 4 above-mentioned synusia materials, identical with the 3 synusia material production methods of introducing previously, it is shape according to final products, size, the difference of desired physical property etc. and different, but generally speaking, following certain methods is roughly arranged, for example, with the above-mentioned sheet material of forming by synthetic resin, the above-mentioned sheet material of forming by polyolefin foam or polyurethane foaming body, above-mentioned sheet material of forming by the improved polyalkene based elastomers and the above-mentioned sheet material of forming by condensate, use the calender roll forming machine, forming machines such as compressing forming machine, carry out heat and fuse, all can obtain 4 above-mentioned synusia materials.

In addition, in the 3rd kind of manufacture method of the present invention, also can on the surface of forming by above-mentioned condensate, top layer, carry out the processing of cotton ginning line, and also can be in printing process, at top layer surface printing literal, pattern, style or the like.In addition, the formation of striped also can be carried out with metal pattern with the vacuum forming that has candy strip.

In the present invention, the thickness of 4 each layers of synusia material, though because of the difference of lamination formed body purposes different, but in general, the thickness of the sandwich layer thickness that preferably is controlled at 0.1-50mm, intermediate layer (I) thickness that preferably is controlled at 0.5-10mm, intermediate layer (II) thickness that preferably is controlled at 0.1-50mm, top layer preferably is controlled in the scope of 5-500 μ m.

Above-mentioned preheat temperature is generally 150-250 ℃.

In the present invention, can 4 above-mentioned synusia materials be carried out vacuum forming, perhaps also can 4 above-mentioned synusia materials be carried out vacuum forming with the convex metal mould that vacuum forming is used with the matrix metal pattern that vacuum forming is used.

By above-mentioned vacuum forming, just can obtain the 1st lamination formed body of the present invention.The finishing of lamination formed body generally is to carry out after above-mentioned vacuum forming.

Introduce the 2nd lamination formed body among the present invention below.

The 2nd lamination formed body involved in the present invention, the sandwich layer of forming by synthetic resin, intermediate layer (II), the condensate that the improved polyalkene based elastomers is formed form the top layer constituted.The difference of it and the 1st lamination formed body involved in the present invention is whether to exist the intermediate layer of being made up of polyolefin foam or polyurethane foaming body (I).So, sandwich layer, intermediate layer (II) and top layer in the 2nd kind of lamination formed body of the present invention, sandwich layer, intermediate layer (II) and the top layer of the 1st kind of lamination formed body of introducing with the front are identical.

The second kind of lamination formed body of the present invention that is made of the 3rd layer on sandwich layer/intermediate layer (II)/top layer can obtain by the 4th, the 5th and the 6th manufacture method of introducing below of the present invention as mentioned above.

At first introduce the production method of the 4th kind of lamination formed body of the present invention.

The manufacture method of the 4th kind of lamination formed body that the present invention relates to, in the manufacture method of the 1st kind of lamination formed body of the present invention that is in front to be introduced, 2 layers of material using the intermediate layer of being made up of above-mentioned improved polyalkene based elastomers (II) and constitute the top layer of being made up of above-mentioned condensate remove to replace 3 synusia materials, and other is all identical with the manufacture method of the 1st kind of lamination formed body among the present invention.

The manufacture method of above-mentioned 2 synusia materials, though because of the difference of the shape of final products, size, desired physical property different, but particularly, manufacture method as 2 above-mentioned synusia materials, be the sheet material that to be formed by above-mentioned improved polyalkene based elastomers and the sheet material of forming by above-mentioned condensate, with forming machines such as calendering roll forming machine, compressing forming machines, carry out heat and melt combination, can obtain 2 above-mentioned synusia materials.In addition, also can allow above-mentioned improved polyalkene based elastomers extrusion molding or roll forming, make its form sheet material, obtain 2 above-mentioned synusia materials after then the sheet material heat of again this sheet material and the above-mentioned condensate that forms sheet material in advance being formed merges.Also having a kind of method is to use the multilayer extruder, allows above-mentioned improved polyalkene based elastomers and above-mentioned polymer extrusion be shaped simultaneously, melts in conjunction with obtaining 2 above-mentioned synusia materials equally by heat.

Then, introduce the manufacture method of the 5th kind of lamination formed body among the present invention.

The present invention relates to the manufacture method of the 5th kind of lamination formed body, be in the manufacture method of the 2nd kind of lamination formed body of the present invention introduced in front, use the intermediate layer (II) be made up of above-mentioned improved polyalkene based elastomers to replace 3 synusia materials with the 2 synusia materials that, the top layer be made up of above-mentioned condensate constitutes, all the manufacture method with the 2nd kind of lamination formed body of the present invention is identical for other.

2 above-mentioned synusia materials are identical with 2 illustrated in the manufacture method of the 4th kind of lamination formed body of the present invention synusia materials.

Introduce the manufacture method of the 6th kind of lamination formed body that the present invention relates to below.

The manufacture method of the 6th kind of lamination formed body among the present invention, be in the manufacture method of the 3rd kind of lamination formed body of above-mentioned the present invention, the 3 synusia materials of using the sandwich layer be made up of above-mentioned synthetic resin, intermediate layer (II) that above-mentioned improved polyalkene based elastomers is formed, top layer that above-mentioned condensate is formed to constitute substitute 4 synusia materials, in addition, all identical with the manufacture method of the 3rd kind of lamination formed body among the present invention.

3 above-mentioned synusia materials are identical with 3 illustrated in the manufacture method of first kind of lamination formed body among the present invention synusia materials.

The effect of invention:

First kind of lamination formed body of the present invention since sandwich layer, polyolefin foam, polyurethane foaming body or the intermediate layer of forming by synthetic resin of being formed by the thermoplastic elastomer foaming body (I), the intermediate layer of being formed by specific improved polyalkene based elastomers (II) and by specific condensate form the top layer constituted, so have performances such as good hear resistance, cold resistance, oil resistivity, solvent resistance, mar proof and anti-scar, simultaneously, also has a kind of sensation of softness.In addition, when the 1st kind of lamination formed body of the present invention has candy strip, not only have above-mentioned various effects, but also have the effect that can form distinct striped.

According to the present invention the 1st, the 2nd and the manufacture method of the 3rd kind of lamination formed body, the 1st kind of lamination formed body of the present invention that can obtain having above-mentioned various effects.In addition, the 2nd kind of lamination formed body of the present invention, since the sandwich layer of forming by synthetic resin, intermediate layer (II), the specific condensate that specific improved polyalkene based elastomers is formed form the top layer constituted, so have various performances such as good hear resistance, cold resistance, oil resistivity, solvent resistance, mar proof and anti-scar, the effect that is imbued with soft feel also arranged simultaneously.In addition, the 2nd kind of lamination formed body of the present invention not only has above-mentioned various effects when candy strip is arranged, and can form the effect of distinct candy strip in addition.

By the of the present invention the 4th, the 5th and the 6th kind of manufacture method, second kind of lamination formed body of the present invention that just can obtain having above-mentioned various effects.

Especially carried out fluffing when the top layer and also had following effect when banding, a kind of soft hand feeling has promptly been arranged.

Above-mentioned of the present invention various lamination formed bodies can be widely used for each method such as automobile interior trim materials such as door trim board, instrument board, roof, various packing case, bag, wall material.

Followingly describe, but the present invention is not only limited in these embodiment according to embodiments of the invention.

At first will be described below by the evaluation method of the degree of depth, soft feeling, mar proof, anti-scar, oil resistivity, solvent resistance, hear resistance and the cold resistance of the cementability of the interlayer in embodiment and the resulting lamination formed body of comparative example, striped.

[evaluation method]

(1) adhesiveness between layers

1. the disbonded test of La Shening

Begin to peel the top layer from an end of test film, at draw speed is under the condition of 25mm/ branch, to the reverse directions stretch release of 180 degree, the width of using test film is divided by at this moment maximum peel load, and resulting value is the interlayer adhesive strength between top layer and intermediate layer (II).

In addition, the evaluation method of the adhesiveness between layers between intermediate layer (II) and intermediate layer (I) or the sandwich layer is to peel off intermediate layer (II), stretches according to above-mentioned method, does disbonded test, then it is estimated.

The evaluation method that adhesiveness between layers between intermediate layer (I) and the sandwich layer is arranged again is to peel off intermediate layer (I), stretches according to above-mentioned method, does disbonded test, then it is estimated.

The size of test film is as follows: long 100mm, wide 25mm, test film take from the position of as shown in Figure 3 lamination formed body.

2. grid disbonded test

Carve 11 roads parallel scar on the surface of sheet material with the interval of 2mm with a sharp shaver, its degree of depth is about about 1mm, and then upwards also carves the same scar in 11 roads at heavy Nogata.

100 square lattices of 2mm like this, have just been formed.Topped firmly these whole 100 grids of the glass gummed paper of using strange kind of Japanese Buddhist nun (ニ チ バ Application) company to produce then, and then peel off this glass gummed paper soon, observe the state of peeling off of this moment.

Peel off the evaluation of state and do not represent (being residual number/100) with being stripped from number that get off, residual/100 in 100 lattices.100/100 expression no one strips down, and 0/100 expression all has been stripped from.

The size of test film is as follows: long 100m, wide 100mm.Test film is that the position from as shown in Figure 3 lamination formed body intercepts.

(2) fringe depths

Measured the distance from peak to bottom-valley of transfer printing at the striped on lamination formed body surface.

(3) soft feeling

Catch and touch the surface of lamination formed body, will feel to be divided into 5 grades.

5 is very soft

4 softnesses

3 is general

2 is hard

1 is stone

(4) mar proof

With C S-11 emery wheel, test for carrying out anti-sliding friction under the condition of 500g at load.Measured the friction consumption of the lamination formed body that rotates after 1000 times.

(5) anti-scar

With bevel-type scratch test machine, with the load of 100 grams, allow the knife edge of blade contact the test portion surface, after rotation under the 1rpm condition, observe its surperficial cut.

Scoring: 1 of A does not see cut

B little or nothing cut

C has tangible cut

(6) oil resistivity

At sheet surface J I S3 oil 1 gram that drips, under 70 ℃ of conditions, place after 168 hours, get back to room temperature, with the flannelette wipe surfaces of exerting oneself, look at whether the surface has abnormal conditions.

Scoring: 1 of A does not see abnormal conditions

B is the vestige of some gonorrhoeas as can be seen

The damage that the C appearance causes owing to peel off, dissolving etc.

(7) solvent resistance

When exerting oneself wipe surfaces, observe the surface and have or not abnormal conditions with the flannelette that contains industrial gasoline.

Scoring: 1 of A does not see abnormal conditions

B is the vestige of some gonorrhoeas as can be seen

C produces the damage that causes owing to peel off, dissolving etc.

(8) hear resistance

From No. 1 type of dumbbell of vertical break-through J I SK6301 tension test sheet of sheet material, under 120 ℃ of temperature, place after 500 hours, get back to room temperature, carry out tension test with the speed that 200mm/ divides, measure the stretching (E Baged) of disrumpent feelings point.In addition, measure the stretching (E Borig) of the preceding disrumpent feelings point of sample of heat ageing in advance, calculated the conservation rate that disrumpent feelings point stretches.

AR（EB）%＝E Baged/E Borig×100

(9) cold resistance

Get a wide 200mm from sheet material, the test film of long 100mm, epidermis side is placed the outside, overlap the two ends of length direction, cripping test sheet, the fixing and rightabout end of kink, under-30 ℃ of situations, place after 20 minutes, the object that a 5kg is heavy is fallen from the height of 5cm and is become the folding part, and observing epidermis then has flawless or cracking phenomena.

The embodiment of first preparation method of the present invention

Embodiment 1

[(ⅰ) making of the three-layer tablet material of forming by polypropylene foam layer, improved polyalkene class elastomer layer and aramid layer]

In nitrogen atmosphere, use Banbury mixer, under 180 ℃, make 80 parts of (weight) ethylene contents 70%(moles), iodine number 12, Mooney viscosity [ML ₁₊₄(100 ℃)] 120 ethene, propylene, 5-ethylidene-2-ENB EVA rubber [below be abbreviated as EPDM(1)] and 20 parts of (weight) MFR(ASTM D 1238-65T, 280 ℃) 13 grams/10 minutes, density 0.91 gram per centimeter ³Polypropylene (below be abbreviated as PP) after mixing 5 minutes, the mixing thing of gained is done slabbing through roll, with the sheet material cutter side of being cut into pellet.

Then, with enjoying the Xie Er mixer, with 100 parts (weight) said side's pellet, 0.3 part of (weight) 1, two (t-butyl peroxy isopropyl) benzene of 3-(below be abbreviated as peroxide (a)], 0.5 part of (weight) divinylbenzene (below be abbreviated as DVB) and 0.5 part of (weight) anhydrous maleic acid (below be abbreviated as MAH) mix.Thereafter, be 50 millimeters single shaft extruder with L/D=30, screw diameter, in nitrogen atmosphere, under 220 ℃, extrude the mixture of gained, make graft-modified polyolefin class elastomer (below be abbreviated as TPE-A).

The diameter that adopts toshiba machine (strain) to make again is 90 millimeters a T mouth mould extrusion shaping machine, and screw rod is full spiral, and L/D=22, extrusion temperature are that 220 ℃, T mouth mould are rack-style, and it is 2.5 meters/minute that rate is drawn speed, with sheet TPE-A is extruded.With the mode of clamping the extrusion sheet shape TPE-A that is molten and polyamide sheet material (eastern レ (strain) makes, nylon 6, trade name:

ミ ラ Application CM1021, thickness are 50 μ m) and polypropylene foam (3 millimeters of eastern レ systems, trade name: PPAN20030, expansion ratio 20, thickness) constitute lamination, pass through a pair roller.At this moment, should make polypropylene and roller temperature is that 60 ℃ roll contacts, and the polyamide sheet material contacts with the roll of room temperature, be made into the three-layer tablet material, wherein the elastomeric thickness of improved polyalkene class is 0.7 millimeter, and the thickness of polyamide is 50 μ m, and the thickness of polypropylene foam is 3 millimeters.

[(ⅱ) the sandwich layer making of thermoplastic elastomer]

In nitrogen atmosphere, under 190 ℃, use Banbury mixer, make 70 parts of (weight) ethylene contents 70%(moles), iodine number 15, Mooney viscosity [ML ₁₊₄(100 ℃)] 120 ethene, propylene-ethylidene norbornene EVA rubber [below be abbreviated as EPDM(1), 30 parts of (weight) MFR(A STM D 1238-65T, 230 ℃) 13 Grams Per Minutes, density 0.91 gram per centimeter ³Polypropylene (below be abbreviated as PP), 10 parts of (weight) butyl rubbers [ェ Star ソ system 11R-065, degree of unsaturation 0.8%(mole), below be abbreviated as 11R] and 30 parts of (weight) paraffin series processes with oil (below be abbreviated as oil) after mixing 5 minutes, the mixing thing that makes gained is by roll, with the slicer side of making pellet.

Then, with enjoying the Xie Er mixer, with 100 parts (weight) said side's pellet, 0.3 part of (weight) 1, two (t-butyl peroxy isopropyl) benzene of 3-(below be abbreviated as peroxide (A)] and 0.5 part of (weight) divinylbenzene (below be abbreviated as DVB) mix.Thereafter, in nitrogen atmosphere, in 220 ℃, extrude said pellet, obtain/10 minutes thermoplastic elastomer of MFR3 gram [below be abbreviated as TPE(1)] with extruder.

[(ⅲ) making of lamination formed body]

The three-layer tablet material that preheating is above-mentioned, the aramid layer that constitutes the three-layer tablet material is placed former, by vacuum forming, it closely is adsorbed on is provided with on the internal face of cavity space of floral designs that the degree of depth is 150 μ m, after pull and stretch processing, closed former from the formpiston side, is filled in also curing in the die cavity to above-mentioned molten sandwich layer with thermoplastic elastomer [TPE(1)] injection moulding by the material injection nozzle of injection moulding machine.TPE(1)] become one with above-mentioned three-layer tablet material, open mould, obtain four layer laminate formed bodies.

Above-mentioned vacuum forming condition is as follows:

Calandria temperature: 360 ℃

Preheating time: 45 seconds

Vacuum pressure: 700mmHg

The condition of above-mentioned injection molded is as follows:

Forming machine: ダ ィ Na メ Le -(bright mechanism is done made)

Forming temperature: 220 ℃

Injection pressure: once press 1000Kg/cm ²

Once press 700Kg/cm ²

Injection moulding speed: maximum

Forming period: 90 seconds/1 cycle

Sprue: direct sprue

(shaped segment length 10mm, wide 10mm, thick 3mm)

About the adhesiveness between layers of the aramid layer (top layer) of four layer laminate formed bodies of gained thus and polypropylene foam layer [intermediate layer (I)], TPE-A layer [intermediate layer (II)] and TPE(1) adhesiveness between layers, fringe depths, soft feeling, mar proof, traumatic resistance, oil resistivity, solvent resistance, hear resistance and the cold resistance of layer (sandwich layer), all connect above-mentioned assessment method evaluation.

Evaluation results is shown in table 1.

Embodiment 2

Sandwich layer is with the thermoplastic elastomer except (ⅰ) three-layer tablet material of making embodiment 1 in order to get off and (ⅱ), and other are all with embodiment 1, obtains four layer laminate formed bodies and it is evaluated.

(ⅰ) making of three-layer tablet material

Except the EPDM(1 during (ⅰ) three-layer tablet material of embodiment 1 is made) and the proportioning of PP change 60 parts of (weight) EPDM(1 into) and 40 parts of (weight) PP, add 20 parts of (weight) butyl rubbers (system, 11R-065) and 40 parts of (weight) paraffin series processes again with outside the oil, with similarly to Example 1 method making graft-modified polyolefin class elastomer (below be abbreviated as TPE-B).Then, with method similarly to Example 1, by said TPE-B and polypropylene foam and polyamide sheet material (ダ ィ セ Le ヒ ェ Le ス system, nylon 12, trade name: ィ

ミ De L2140, thick 50 μ m), make the three-layer tablet material, wherein the thickness of improved polyalkene class elastomer layer (TPE-B layer) is that the thickness of 0.7m, polypropylene foam layer is 3mm, the thickness of aramid layer is 50 μ m.

(ⅱ) the sandwich layer making of thermoplastic elastomer

With enjoying the Xie Er mixer, make 60 parts (weight) [wherein 43 parts (weight) is oil for EPDM17 part (weight)] ethylene contents 78%(mole), iodine number 10, Mooney viscosity [ML ₁₊₄(100 ℃)] granular ethene, propylene-ethylidene norbornene EVA rubber [below be abbreviated as EPDM(2)] and 40 parts of (weight) PP and 0.5 part of (weight) 2 of 160,40 parts of (weight) oily exhibition amounts, 5-dimethyl-2,5-two (t-butyl peroxy) is abbreviated as peroxide (B) below hexin-3(] mix.Thereafter, in nitrogen atmosphere under 220 ℃, with watt that (ワ-Na-) biaxial extruder (L/D=43, mesh form, rotation, three screw types) in the same way the mixture of gained is extruded, obtained/10 minutes thermoplastic elastomer of MFR15 gram [below be abbreviated as TPE(2)].

Evaluation result is shown in table 1.

Embodiment 3

Except with melt index (MI) (A STM D-1238-65T, 230 ℃) 13, density 0.91 gram per centimeter ³Polypropylene [below be abbreviated as PP(1)] substitute TPE(1), outside (ⅰ) three-layer tablet material of making embodiment 1 by following method was made, row with similarly to Example 1 the time obtained four layer laminate formed bodies and it is evaluated.

(ⅰ) making of three-layer tablet material

Making for (ⅰ) three-layer tablet material of embodiment 1, except EPDM(1) and the proportioning of PP be adjusted into 80 parts of (weight) EPDM(1) and 20 parts of (weight) PP, add 10 parts of (weight) butyl rubbers (ェ ッ ソ system, 11R-065) with 30 parts of (weight) paraffin series technical process oil, make the elastomeric side's pellet of unmodified polyolefin class, substitute with epihydric alcohol methylpropenoic acid ester that anhydrous maleic acid is made graft-modified polyolefin class elastomer (below be abbreviated as TPE-C) and (eastern レ (strain) makes with polyester sheet, Le ミ ラ-, thick 50 μ m) substitute outside the polyamide sheet material, carry out with method similarly to Example 1, make the three-layer tablet material, wherein the thickness of improved polyalkene class elastomer layer (TPE-C layer) is 0.7mm, the thickness of polypropylene foam layer is 3mm, and the thickness of polyester is 50 μ m.

Evaluation result is shown in table 1.

Embodiment 4

Except substituting TPE(1 with/10 minutes polypropylene of the MFR5 gram that contains 10% micro mist talcum and 10% short fiber glass fibre [below be abbreviated as PP(2)]), carry out the making of (ⅰ) three-layer tablet material of embodiment 1 with method similarly to Example 1, obtain four layer laminate formed bodies and it is evaluated.

(1) making of three-layer tablet material

Making for (ⅰ) three-layer tablet material of embodiment 1, make graft-modified polyolefin class elastomer (below be abbreviated as TPE-D) except substitute anhydrous maleic acid with hydroxy propyl methacrylate, and with outside the alternative polyamide sheet material of polyurethane sheet (Japanese polyurethane system, thermoplastic polyurethane P26SRNAT, thick 50 μ m), make the three-layer tablet material with method similarly to Example 1, wherein the thickness of improved polyalkene class elastomer layer (TPE-D layer) is 0.7mm, the thickness of polypropylene foam layer is 3mm, and the thickness of thermoplastic polyurethane layer is 50 μ m.

Evaluation result is shown in table 1.

Embodiment 5

In the making of embodiment 1 (ⅰ) three-layer tablet material, 80 parts of (weight) graft-modified polyolefin class elastomers (TPE-A) of embodiment 1 adopt 20 parts of (weight) low density polyethylene (LDPE) [density 0.917 gram per centimeters relatively ³, melt index (MI) 6.5(190 ℃)] do and mix, supply with outside the T mouth mould extrusion moulding machine, similarly to Example 1 carry out thereafter, make the three-layer tablet material, wherein the thickness of improved polyalkene class elastomer layer (TPE-E layer) is 0.7mm, and the thickness of polypropylene foam layer is 3mm, and the thickness of aramid layer is outside the 50 μ m, with method similarly to Example 1, obtain four layer laminate formed bodys and it is evaluated.

Evaluation result is shown in table 1.

Comparative example 1

In embodiment 1, except the flexible vinyl chloride sheet material (thick 0.75mm) that contains dioctyl phthalate with 50 parts (weight) substitutes the three-layer tablet material,, obtain three layer laminate formed bodies and it is evaluated with method similarly to Example 1.

Evaluation result is shown in table 1.

Comparative example 2

In embodiment 1,,, obtain three layer laminate formed bodies and it is evaluated with method similarly to Example 1 except the single sheet with the TPE-A of folded polyamide sheet material layer substitutes the three-layer tablet material.

Evaluation result is shown in table 1.

Comparative example 3

In the making of embodiment 1 (ⅰ) three-layer tablet material, except not carrying out graft modification, with similarly to Example 1 method make three-layer tablet material thereafter, wherein the thickness of unmodified polyolefin class elastomer layer (TPE-F layer) is 0.7mm, the thickness of polypropylene foam layer is 3mm, the thickness of aramid layer is outside the 50 μ m, with method similarly to Example 1, obtains four layer laminate formed bodies and it is evaluated.

Evaluation result is shown in table 1.

The embodiment of second preparation method of the present invention

Embodiment 11

Except making,, obtain four layer laminate formed bodys and it is evaluated with method similarly to Example 1 by following (ⅲ) laminated molded article that carries out embodiment 1 like that.

(ⅲ) making of laminated molded article

The three-layer tablet material of preheating embodiment 1, the aramid layer that constitutes the three-layer tablet material is placed former one side, by vacuum forming, it closely is adsorbed on is provided with on the internal face of cavity space of floral designs that the degree of depth is 150 μ m, after pull and stretch processing, the sandwich layer of molten is placed on the three-layer tablet material equably with thermoplastic elastomer [TPE(1)], closed formpiston, make TPE(1) solidify with above-mentioned three-layer tablet material and become one, open mould, obtain four layer laminate formed bodies.

Above-mentioned vacuum forming condition is identical with vacuum forming condition among the embodiment 1.

The condition of above-mentioned impact moulding is as follows:

Make-up machine: pond shellfish 1 SM-300

Screw diameter: φ 50mm

Resin temperature: 230 ℃

Press pressure: 200Kg/cm ²

Forming period: 50 seconds/1 cycle

Drip molding: long 500mm, wide 500mm, thick 3mm

Evaluation result is shown in table 2

Embodiment 12

In embodiment 11, except with the three-layer tablet material of embodiment 2 and the TPE(2 of embodiment 2) the three-layer tablet material (the three-layer tablet material of embodiment 1) of alternate embodiment 11 and TPE(1), with method similarly to Example 11, obtain four layer laminate formed bodys and it is evaluated.

Evaluation result is shown in table 2.

Embodiment 13

In embodiment 11, except with the three-layer tablet material of embodiment 3 and melt index (MI) (ASTM D1238-65T, 230 ℃) 3, density 0.91 gram per centimeter ³Polypropylene [below be abbreviated as PP(3)] alternate embodiment 11 three-layer tablet material (the three-layer tablet material of embodiment 1) and TPE(1) outside, with method similarly to Example 11, obtain four layer laminate formed bodys and it evaluated.

Evaluation result is shown in table 2.

Embodiment 14

In embodiment 11, except with the three-layer tablet material of embodiment 4 and contain 15% micro mist talcum, the three-layer tablet material (the three-layer tablet material of embodiment 1) of/10 minutes polypropylene of the MFR0.7 of 15% short glass fiber gram [below be abbreviated as PP(4)] alternate embodiment 11 and TPE(1) outside, with method similarly to Example 11, obtain four layer laminate formed bodys and it is evaluated.

Evaluation result is shown in table 2.

Embodiment 15

In embodiment 11, except with the three-layer tablet material of embodiment 5 and the PP(4 of embodiment 4) the three-layer tablet material (the three-layer tablet material of embodiment 1) of alternate embodiment 11 and TPE(1), with method similarly to Example 11, obtain four layer laminate formed bodies and it is evaluated.

Evaluation result is shown in table 2.

Comparative example 11

In embodiment 11,,, obtain three layer laminate formed bodys and it is evaluated with method similarly to Example 11 except substituting the three-layer tablet material with the flexible vinyl chloride sheet material (thick 0.75mm) of comparative example 1.

Evaluation result is shown in table 2.

Comparative example 12

In embodiment 11,,, obtain three layer laminate formed bodys and it is evaluated with method similarly to Example 11 except the single sheet with the TPE-A of folded aramid layer substitutes the three-layer tablet material.

Evaluation result is shown in table 2.

Comparative example 13

In embodiment 11, except three-layer tablet material (the three-layer tablet material of embodiment 1),, obtain four layer laminate formed bodys and it is evaluated with method similarly to Example 11 with the three-layer tablet material alternate embodiment 11 of comparative example 3.

Evaluation result is shown in table 2.

The embodiment of the 3rd preparation method of the present invention

Embodiment 21

[making of four synusia materials]

The diameter made from toshiba machine (strain) is 90 millimeters a T mouth mould extrusion shaper, screw rod is full spiral, L/D=22, extrusion temperature is 220 ℃, T mouth mould is a rack-style, hauling speed is 2.5 meters/minute, makes TPE-A and the TPE(1 of embodiment 1 with sheet) extrude and, pass through a pair roller with the layer-by-layer state of the polypropylene foam of polyamide sheet material/TPE-A/ embodiment 1 of embodiment 1/TPE(1) constitute.At this moment, making TPE(1) sheet material and roller temperature be that 60 ℃ roll contacts, and the polyamide sheet material contacts with the roll of room temperature, make four synusia materials, wherein the thickness of thermoplastic elastomer layer [TPE(1)] is 2mm, the thickness of polypropylene foam layer is 3mm, and the thickness of improved polyalkene class elastomer layer (TPE-A layer) is 0.7mm, and the thickness of aramid layer is 50 μ m.

[making of laminated molded article]

The four synusia materials that preheating is above-mentioned place former one side to the aramid layer that constitutes four synusia materials, by vacuum forming, it closely is adsorbed on is provided with on the internal face of cavity space of floral designs that the degree of depth is 150 μ m, after pull and stretch processing, open mould, obtain four layer laminate formed bodies.

Above-mentioned vacuum-formed condition is as follows:

Calandria temperature: 360 ℃

Preheating time: 100 seconds

Vacuum pressure: 700mmHg

By above-mentioned assessment method, evaluate aramid layer (top layer) and TPE-A layer in the four layer laminate formed bodies of gained thus [interlayer adhesion of intermediate layer (II), polypropylene layer [intermediate layer (I)] and TPE(1) interlayer adhesion, pattern depth, soft feeling, mar proof, traumatic resistance, oil resistivity, solvent resistance, hear resistance and the cold resistance of layer (sandwich layer).

Evaluation result is shown in table 3.

Embodiment 22

In embodiment 21, except the TPE-B with embodiment 2 substitutes TPE-A, with the polyamide sheet material (the polyamide sheet material of embodiment 1) of the polyamide sheet material alternate embodiment 21 of embodiment 2 and with the TPE(2 of embodiment 2) substitute TPE(1) outside, with method similarly to Example 21, obtain four layer laminate formed bodys and it is evaluated.

Evaluation result is shown in table 3.

Embodiment 23

In embodiment 21, except the TPE-C with embodiment 3 substitutes TPE-A, with the polyamide sheet material (the polyamide sheet material of embodiment 1) of the polyester sheet alternate embodiment 21 of embodiment 3 and with the PP(1 of embodiment 3) substitute TPE(1) outside, with method similarly to Example 21, obtain four layer laminate formed bodies and it is evaluated.

Evaluation result is shown in table 3.

Embodiment 24

In embodiment 21, except the TPE-D with embodiment 4 substitutes TPE-A, with the polyamide sheet material (the polyamide sheet material of embodiment 1) of the polyurethane sheet alternate embodiment 21 of embodiment 4 and with the PP(2 of embodiment 4) substitute TPE(1) outside with similarly to Example 21 method, obtain four layer laminate formed bodies and it evaluated.

Evaluation result is shown in table 3.

Embodiment 25

In embodiment 21,,, obtain four layer laminate formed bodies and it is evaluated with method similarly to Example 21 except substituting the TPE-A with the TPE-E of embodiment 5.

Evaluation result is shown in table 3.

Comparative example 21

In embodiment 21,,, obtain three layer laminate formed bodies and it is evaluated with method similarly to Example 21 except substituting the polyamide sheet material with the flexible vinyl chloride sheet material of comparative example 1 and without the TPE-A.

Evaluation result is shown in table 3.

Comparative example 22

In embodiment 21, except the TPE-A of embodiment 1 substitutes the polyamide sheet material, and without TPE-A as outside intermediate layer (II), with method similarly to Example 21, obtain three layer laminate formed bodies and it evaluated.

Evaluation result is shown in table 3.

Comparative example 23

In embodiment 21,,, obtain four layer laminate formed bodies and it is evaluated with method similarly to Example 21 except substituting the TPE-A with the TPE-F of comparative example 3.

Evaluation result is shown in table 3.

The embodiment of the 4th preparation method of the present invention

Embodiment 31

[(ⅰ) making of the two synusia materials of forming by improved polyalkene class elastomer layer and aramid layer]

In nitrogen atmosphere, under 180 ℃, use Banbury mixer, make 80 parts of (weight) ethylene contents 70%(moles), iodine number 12, Mooney viscosity [ML ₁₊₄(100 ℃)] 120 ethene, propylene, 5-ethylidene-2-ENB EVA rubber [EPDM(1)] and 20 parts of (weight) MFR(A STM D1238-65T, 230 ℃) 13 grams/10 parts, density 0.91 gram per centimeter ³Polypropylene (PP), after mixing 4 minutes, the mixing thing of gained is done slabbing through roll, with the sheet material cutter side of being cut into pellet.

Then, with enjoying the Xie Er mixer, with 100 parts (weight) said side's pellet, 0.3 part of (weight) 1, two (t-butyl peroxy isopropyl) benzene [peroxide (A)] of 3-, 0.5 part of (weight) divinylbenzene (DVB) and 0.5 part of (weight) anhydrous maleic acid (MAH) mix.Thereafter, be 50 millimeters single shaft extruder with L/D=30, screw diameter, in nitrogen atmosphere, under 220 ℃, extrude the mixture of gained, make graft-modified polyolefin class elastomer (TPE-A of embodiment 1).

The diameter that adopts toshiba machine (strain) to make again is 90 millimeters a T mouth mould extrusion shaping machine, and screw rod is full spiral, and L/D=22, extrusion temperature are 220 ℃, and T mouth mould is a rack-style, and hauling speed is 2.5 meters/minute, with sheet TPE-A is extruded.Make the extrusion sheet shape TPE-A that is molten and embodiment 1 the polyamide sheet material (eastern レ (strain) system, nylon 6, trade name:

ミ ラ Application CM1021, thick 50 μ m) become the state of lamination, pass through a pair roller.At this moment, TPE-A sheet material and roller temperature are that 60 ℃ roll contacts, and polyamide contacts with the roll of room temperature, makes two synusia materials, and wherein the thickness of improved polyalkene class elastomer layer (TPE-A layer) is 0.7mm, and the thickness of aramid layer is 50 μ m.

[(ⅱ) the sandwich layer making of thermoplastic elastomer]

In nitrogen atmosphere, under 190 ℃, use Banbury mixer, make 70 parts of (weight) ethylene contents 70%(moles), iodine number 15, Mooney viscosity [ML ₁₊₄(100 ℃)] 120 ethene, propylene, ethylidene norbornene EVA rubber [EPDM(1)], 30 parts of (weight) MFR(A STM D1238-65T, 230 ℃) 13 grams/10 parts, density 0.91 gram per centimeter ³Polypropylene (PP), 10 parts of (weight) butyl rubbers [ェ ッ ソ system 11R-065, degree of unsaturation 0.8%(mole), below be abbreviated as 11R] and 30 parts of (weight) paraffin series processes oil, after mixing 5 minutes, the mixing thing of gained is done slabbing through roll, with the sheet material cutter side of being cut into pellet.

Then, with enjoying the Xie Er mixer, with the square pellet of 100 parts of (weight) gained, 0.3 part of (weight) 1, two (t-butyl peroxy isopropyl) benzene [peroxide (A)] of 3-, 0.5 part of (weight) divinylbenzene (DVB) mix.Thereafter, use extruder, in nitrogen atmosphere, under 220 ℃, pellet is extruded, but obtain/10 minutes heat property elastomer of MFR3 gram [TPE(1 of embodiment 1)].

[(ⅲ) making of laminated molded article]

The two synusia materials that preheating is above-mentioned, the aramid layer that constitutes two synusia materials is placed former one side, by vacuum forming, it closely is adsorbed on is provided with on the internal face of cavity space of floral designs that the degree of depth is 150 μ m, after pull and stretch processing, closed former is from formpiston one side, by the material injection nozzle of injection moulding machine, be filled in above-mentioned molten sandwich layer in the die cavity with thermoplastic elastomer [TPE(1)] injection moulding and solidify.TPE(1) become one with above-mentioned two synusia materials, open mould, obtain three layer laminate formed bodies.

Above-mentioned vacuum-formed condition is as follows:

Calandria temperature: 360 ℃

Preheating time: 45 seconds

Vacuum pressure: 700mm Hg

The condition of above-mentioned injection molded is as follows:

Make-up machine: ダ ィ Na メ Le -(bright mechanism is done made)

Forming temperature: 220 ℃

Injection pressure: once press 1000kg/cm ²

Secondary is pressed 700kgcm ²

Injection moulding speed: maximum

Molding cycle: 90 seconds/1 cycle

Sprue: direct sprue

(shaping segment lenght 10mm, wide 10mm, thick 3mm)

According to above-mentioned assessment method, evaluation is by the adhesiveness between layers of the polyamide (top layer) in three layers of laminated molded article of forming of gained and TPE-A layer [intermediate layer (II)], TPE-A layer [intermediate layer (II)] and TPE(1) adhesiveness between layers, pattern depth, soft feeling, mar proof, traumatic resistance, oil resistivity, solvent resistance, hear resistance and the cold resistance of layer (sandwich layer).

Evaluation result is shown in table 4.

Embodiment 32

Except by the making of following (ⅰ) two synusia materials that carry out embodiment 31 and (ⅱ) sandwich layer, obtain three layer laminate formed bodies and it evaluated with the method same with the making of thermoplastic elastomer with embodiment 31.

(ⅰ) making of two synusia materials

In the making of embodiment 31 (ⅰ) two synusia materials, except EPDM(1) change 60 parts of (weight) EPDM(1 into the proportioning of PP), 40 parts of (weight) PP and add 20 parts of (weight) butyl rubbers (ェ ッ ソ make, 11R-065) and 40 parts of (weight) paraffin series processes usefulness oil outside, with the method same, make graft-modified polyolefin class elastomer (TPE-B of embodiment 2) with embodiment 31.Then, by polyamide sheet material (ダ ィ セ Le ヒ ェ Le ス making, nylon 12, the trade name: ダ ィ of said TPE-B and embodiment 2

ミ De L2140, thick 50 μ m), with the method same, make two synusia materials with embodiment 31, wherein the thickness of improved polyalkene class elastomer (TPE-B) is 0.7mm, the thickness of aramid layer is 50 μ m.

(ⅱ) the sandwich layer making of thermoplastic elastomer

With enjoying the Xie Er mixer, make 60 parts (weight) [43 parts of (weight) EPDM, 17 parts of (weight) oil] ethylene contents 78%(mole), iodine number 10, Mooney viscosity [ML ₁₊₄(100 ℃)] the granular ethene, propylene, ethylidene norbornene EVA rubber [EPDM(2)] of 160,40 parts of (weight) oily exhibition amounts, 40 parts of (weight) PP and 0.5 part of (weight) 2,5-dimethyl-2,5-two (t-butyl peroxy) hexin-3[peroxide (B)] mix.Then, in nitrogen atmosphere under 220 ℃,, the mixture of gained is extruded with watt that biaxial extruder (L/D=43, mesh form, rotation, three screw types) in the same way.Obtain/10 minutes thermoplastic elastomer of MFR15 gram [TPE(2 of embodiment 2)].

Evaluation result is shown in table 4.

Embodiment 33

By the following making of carrying out (ⅰ) two synusia materials of embodiment 31, except with melt index (MI) (A STM D1238-65T, 230 ℃) 13, density 0.91 gram/cm ³Polypropylene [PP(1 of embodiment 3)] substitute TPE(1) outside, with the method same, obtain three layer laminate formed bodies and it evaluated with embodiment 31.

(ⅰ) making of two synusia materials

In the making of embodiment 31 (ⅰ) two synusia materials, except EPDM(1) change 80 parts of (weight) EPDM(1 into the proportioning of PP), 20 parts of (weight) PP, (ェ ッ ソ makes to add 10 parts of (weight) butyl rubbers again, 11R-065) and 30 parts of (weight) paraffin series processes with oily and make the square pellet of unmodified poly-hydrocarbon elastomer, substitute that anhydrous maleic acid is made graft-modified polyolefin class elastomer (TPE-C of embodiment 3) and with polyester sheet (eastern レ (strain) making of embodiment 3 with epihydric alcohol methylpropenoic acid ester, thick 50 μ m) substitute outside the polyamide sheet material, with the method same with embodiment 31, make two synusia materials, wherein the thickness of improved polyalkene class elastomer layer (TPE-C layer) is 0.7mm, and the thickness of polyester layer is 50 μ m.

Evaluation result is shown in table 4.

Embodiment 34

By the following making of carrying out (ⅰ) two synusia materials of embodiment 31, and except using/10 minutes the polypropylene (PP(2) of MFR5 gram that contains 10% micro mist talcum, 10% short glass fiber] alternative TPE(1), with the method same, obtain three layer laminate formed bodies and it is evaluated with embodiment 31.

(ⅰ) making of two synusia materials

In the making of embodiment 31 (ⅰ) two synusia materials, with the alternative anhydrous maleic acid making graft-modified polyolefin class elastomer (TPE-D of embodiment 4) of hydroxy propyl methacrylate and with outside the alternative polyamide sheet material of the poly-propylhomoserin sheet material (making of Japanese polyurethane company, thermoplastic polyurethane P26SRNAT, thick 50 μ m) of embodiment 4, with the method same with embodiment 31, make two synusia materials, the thickness 0.7mm of improved polyalkene class elastomer layer (TPE-D layer) wherein, the thickness of thermoplastic polyurethane layer is 50 μ m.

Evaluation result is shown in table 4.

Embodiment 35

In the making of embodiment 31 (ⅰ) two synusia materials, 80 parts of (weight) graft-modified polyolefin class elastomers (TPE-A) of embodiment 31 adopt 20 parts of (weight) low density polyethylene (LDPE) [density 0.91 gram per centimeters relatively ³, melt index (MI) 6.5(190 ℃)] do and mix, supply with T mouth mould extruder, with embodiment 31 equally carry out thereafter, make two synusia materials, wherein the thickness of improved polyalkene class elastomer layer (TPE-E layer) is 0.7mm, the thickness of aramid layer is outside the 50 μ m, with the method same with embodiment 31, obtains three layer laminate formed bodies and it is evaluated.

Evaluation result is shown in table 4.

Comparative example 31

In embodiment 31, except the flexible vinyl chloride sheet material (thick 0.75mm) with the comparative example 1 that contains 50 parts of (weight) dioctyl phthalates substitutes the two synusia materials, with the method same, obtain two layer laminate formed bodies and it is evaluated with embodiment 31.

Evaluation result is shown in table 4.

Comparative example 32

In embodiment 31,,, obtain two layer laminate formed bodies and it is evaluated with the method same with embodiment 31 except the single sheet with the TPE-A of folded polyamide sheet material layer substitutes the two synusia materials.

Evaluation result is shown in table 4.

Comparative example 33

In the making of embodiment 31 (ⅰ) two synusia materials, except not carrying out graft modification, thereafter to make two synusia materials with the same method of embodiment 31, wherein the thickness of unmodified polyolefin class elastomer layer (TPE-F layer) is 0.7mm, the thickness of aramid layer is outside the 50 μ m, with the method same, obtain three layer laminate formed bodies and it is evaluated with embodiment 31.

Evaluation result is shown in table 4.

The embodiment of the 5th preparation method of the present invention

Embodiment 41

Except making,, obtain three layer laminate formed bodys and it is evaluated with the method same with embodiment 31 by following (ⅲ) lamination formed body that carries out embodiment 31.

(ⅲ) making of lamination formed body

The two synusia materials of preheating embodiment 31, the aramid layer that constitutes two synusia materials is placed former one side, by vacuum forming, it closely is adsorbed on is provided with on the internal face of cavity space of floral designs that the degree of depth is 150 μ m, after pull and stretch processing, the sandwich layer of molten is placed on the two synusia materials equably with thermoplastic elastomer [TPE(1)], closed formpiston, make TPE(1) solidify with two above-mentioned synusia materials and become one, open mould, obtain three layer laminate formed bodies.

The condition of above-mentioned vacuum forming is as follows:

Forming machine: pond shellfish 1 SM-300

Screw diameter: φ 50mm

Resin temperature: 230 ℃

Press pressure: 200kg/cm ²

Molding cycle: 50 seconds/1 cycle

Profiled member: length 500mm, width 500mm, thickness 3mm

Evaluation result is shown in table 5.

Embodiment 42

In embodiment 41, except with the two synusia materials of embodiment 32 and the TPE(2 of embodiment 32) the two synusia materials (the two synusia materials of embodiment 31) of alternate embodiment 41 and TPE(1), with the method same, obtain three layer laminate formed bodies and it is evaluated with embodiment 41.

Evaluation result is shown in table 5.

Embodiment 43

In embodiment 41, except with the two synusia materials of embodiment 33 and melt index (MI) (A STM D1238-65T, 230 ℃) 3, density 0.91 gram per centimeter ³Polypropylene [below be abbreviated as PP(3)] alternate embodiment 41 two synusia materials (the two synusia materials of embodiment 31) and TPE(1) outside, with the method same, obtain three layer laminate formed bodys and it evaluated with embodiment 41.

Evaluation result is shown in table 5.

Embodiment 44

In embodiment 41, except with the two synusia materials of embodiment 34 and contain 15% micro mist talcum, 15% short glass fiber/10 minutes polypropylene of MFR0.7 gram [below be abbreviated as PP(4)] alternate embodiment 41 two synusia materials (the two synusia materials of embodiment 31) and TPE(1), with the method same, obtain three layer laminate formed bodies and it is evaluated with embodiment 41.

Evaluation result is shown in table 5.

Embodiment 45

In embodiment 41, except with the two synusia materials of embodiment 35 and the PP(4 of embodiment 44) the two synusia materials (the two synusia materials of embodiment 31) of alternate embodiment 41 and TPE(1), with the method same, obtain three layer laminate formed bodys and it is evaluated with embodiment 41.

Evaluation result is shown in table 5.

Comparative example 41

In embodiment 41, except substituting the two synusia materials,, obtain two layer laminate formed bodys and it is evaluated with the method same with embodiment 41 with the flexible vinyl chloride sheet material (thick 0.75mm) of comparative example 31.

Evaluation result is shown in table 5.

Comparative example 42

In embodiment 41,,, obtain two layer laminate formed bodys and it is evaluated with the method same with embodiment 41 except the single sheet with the TPE-A of folded polyamide sheet material layer substitutes the two synusia materials.

Evaluation result is shown in table 5.

Comparative example 43

In embodiment 41, except two synusia materials (the two synusia materials of embodiment 31),, obtain three layer laminate formed bodys and it is evaluated with the method same with embodiment 41 with two synusia material alternate embodiments 41 of comparative example 33.

Evaluation result is shown in table 5.

Embodiment 51

The diameter made from toshiba machine (strain) is 90 millimeters a T mouth mould extrusion moulding machine, screw rod is full spiral, L/D=22, extrusion temperature is 220 ℃, T mouth mould is a rack-style, hauling speed is 2.5 meters/minute, makes TPE-A and the TPE(1 of embodiment 31 with sheet) extrude and, pass through a pair roller with the layer-by-layer state of the polyamide sheet material of embodiment 31/TPE-A/TPE(1) constitute.At this moment, making TPE(1) sheet material and roller temperature be that 60 ℃ roll contacts, and the polyamide sheet material contacts with the room temperature roll, make the three-layer tablet material, wherein the thickness of thermoplastic elastomer layer [TPE(1) layer] is 2mm, the thickness of improved polyalkene class elastomer layer (TPE-A layer) is 0.7mm, and the thickness of aramid layer is 50 μ m.

[making of lamination formed body]

The three-layer tablet material that preheating is above-mentioned places former one side to the aramid layer that constitutes the three-layer tablet material, by vacuum forming, it closely is adsorbed on is provided with on the internal face of cavity space of floral designs that the degree of depth is 150 μ m, after pull and stretch processing, open mould, obtain four layer laminate formed bodies.

Above-mentioned vacuum-formed condition is as follows:

Calandria temperature: 360 ℃

Preheating time: 100 seconds

Vacuum pressure: 700mmHg

By above-mentioned assessment method, evaluate aramid layer (top layer) and TPE-A[intermediate layer (II) in the four layer laminate formed bodies of gained thus] adhesiveness between layers, polypropylene layer [intermediate layer (I)] and TPE(1) adhesiveness between layers, pattern depth, soft feeling, mar proof, traumatic resistance, oil resistivity, solvent resistance, hear resistance and the cold resistance of layer (sandwich layer).

Evaluation result is shown in table 6.

Embodiment 52

In embodiment 51, except the TPE-B with embodiment 32 substitutes TPE-A, with the polyamide sheet material (the polyamide sheet material of embodiment 31) of the polyamide sheet material alternate embodiment 51 of embodiment 32 and with the TPE(2 of embodiment 32) substitute TPE(1) outside, with the method same, obtain three layer laminate formed bodies and it is evaluated with embodiment 51.

Evaluation result is shown in table 6.

Embodiment 53

In embodiment 51, except the TPE-C with embodiment 33 substitutes TPE-A, with the polyamide sheet material (the polyamide sheet material of embodiment 31) of the polyester sheet alternate embodiment 51 of embodiment 33 and with the PP(1 of embodiment 33) substitute TPE(1) outside, with the method same, obtain three layer laminate formed bodies and it is evaluated with embodiment 51.

Evaluation result is shown in table 6.

Embodiment 54

In embodiment 51, except the TPE-D with embodiment 34 substitutes TPE-A, with the polyamide sheet material (the polyamide sheet material of embodiment 31) of the polyurethane sheet alternate embodiment 51 of embodiment 34 and with the PP(2 of embodiment 34) substitute TPE(1) outside, with the method same, obtain three layer laminate formed bodies and it is evaluated with embodiment 51.

Evaluation result is shown in table 6.

Embodiment 55

In embodiment 51, except substituting the TPE-A,, obtain three layer laminate formed bodies and it is evaluated with the method same with embodiment 51 with the TPE-E of embodiment 35.

Evaluation result is shown in table 6.

Comparative example 51

In embodiment 51, except substituting the polyamide sheet material with the flexible vinyl chloride sheet material of comparative example 31 and do not use the TPE-A, the method same with embodiment 51 obtains two layer laminate formed bodies and it evaluated.

Evaluation result is shown in table 6.

Present embodiment is the same with embodiment 51, and different is that it does not use the polyamide sheet material, and is to use the TPE-A of embodiment 31, and it does not use the TPE as intermediate layer (II) yet in addition.Obtained the formed body of 2 layer laminate at last, and it has been done evaluation

Evaluation result is shown in table 6.

Comparative example 53

Present embodiment is identical with embodiment 51, and different is that it does not use TPE-A, and is to use the TPE-F of comparative example 33.Obtain the formed body of 3 layer laminate at last, and it has been done evaluation.

Evaluation result is shown in table 6

Embodiment 56

[the feed particles TPE3 of the feed particles TPE-A of intermediate layer (II), intermediate layer (I) and the feed particles TPE(1 of sandwich layer) manufacturing]

<TPE（3）>

Isotactic polypropylene resin [melt flow: 13g/10 branch (230 ℃)] 25 weight portions

Ethylene, propylene ethylidene norbornene ter-polymer rubber [ethene unit/propylene unit (mol ratio): 78/22, iodine value: 15, Mooney (Mooney) is viscosity ML(121 ℃): 61] 75 weight portions.

Adopt the Banbury muller, under nitrogen environment, the butyl rubber (company makes IIR065) of 25 weight portions and the naphthene series operation finish of 30 weight portions were mixed under 180 ℃ 5 minutes, with slicer the thing that mixes of gained is cut into the horn shape tablet then.

Then, adopt Λ Application シ ェ Le muller, in tablet 100 weight portions of this horn shape, mix [wherein into the mixture of 1 weight portion, 20 weight % are 1, two (the tert-butyl peroxy isopropyl base) benzene of 3-, 30 weight % are divinylbenzene, 50 weight % are paraffin series mineral oil.) and adopt extruder under nitrogen environment, under 220 ℃, to extrude, thereby produce the particle of thermoplastic elastomer [TPE(3)].

[manufacturings of 4 layer laminate sheet materials]

At first, adopt Λ Application シ ェ Le muller in the TPE3 of 100 weight portions, to mix into the azodicarbonamide (ADCA) of 20 weight portions and the cyanuric acid triolefin isopropyl ester (TAIC) of 0.1 weight portion, L/D=22, extrusion temperature is that 180 ℃ of hauling speeds are the 5m/ branch, thereby makes the not foam sheet that thickness is 0.5mm.

Then, adopt that Toshiba makes by 90mm φ, two layers of T mouth of crosshead mould extrusion shaper that 40mm φ constitutes, TPE-A is supplied in the extruder of 90mm φ, poly-imide resin (ダ ィ セ Le ヒ ェ Le ス, nylon 12 L2140) be supplied in the extruder of 40mm φ, at extrusion temperature is 220 ℃, hauling speed is under the condition of 2.5m/ branch, be squeezed into two synusia materials, not foam sheet at the TPE-AL superimposed layer TPE3 of the melting state that is in that is extruded out, make it by a pair roller, thereby the thickness of having made aramid layer is 30 μ m, TPE-A is 0.7mm, TPE3 is the 3 synusia materials of 0.5mm.

Then, adopt the T mouth mould extrusion shaper of the 90mm φ of Toshiba's manufacturing, at extrusion temperature is that 220 ℃, hauling speed are the following TPE(1 of condition that 2.5m/ divides) be squeezed into sheet material, make the sheet TPE(1 that is in the melting state that squeezes out) contact with not foaming layer one side of the TPE3 of the previous 3 synusia materials of making and make it by a pair roller, be that 30 μ m, TPE-A are that 0.7mm, TPE3 are 0.5mm, TPE(1 thereby make aramid layer) be the 4 synusia materials of 3mm.

[the not foaming of foam sheet]

It is to reach 4 minutes in 240 ℃ the air-oven that above-mentioned 4 synusia materials are placed on temperature, makes not foam sheet foaming of TPE3, is that 30 μ m, TPE-A are that 0.7mm, TPE3 are 1.0mm, TPE(1 thereby make aramid layer) be the 4 synusia materials of 3mm.

[manufacturing of lamination formed body]

Above-mentioned 4 synusia materials are given heat, make the aramid layer that constitutes 4 synusia materials be in former one side, utilize vacuum forming to make it to attract adherence executing on the internal face of die cavity of candy strip that the degree of depth is 150 μ m in former, carry out opening metal pattern after the extrusion process, thereby obtained the lamination formed body that constitutes by 4 layers.

In addition, above-mentioned vacuum-formed condition is as follows:

Heating-up temperature: 360 ℃

Preheat the time: 100 seconds

Vacuum is pressed: 700mmHg

As for so obtain [intermediate layer (II) mutual adhesiveness, foaming TPE3 layer [intermediate layer (I)] and TPE(1) layer (sandwich layer) mutual adhesiveness, fringe depths, soft feeling, abrasion performance, anti-trace, oil resistivity, solvent resistance, hear resistance and cold resistance, all available aforesaid evaluation method is estimated by the aramid layer (epidermal area) in 4 layers of lamination formed body that constitutes and TPE-A layer.

That estimates the results are shown in table 7.

Embodiment 57-60

Except the feed particles of the intermediate layer (II) that makes embodiment 56 and sandwich layer and top layer as table 7, other is all identical with embodiment 56.

Again, the TPE-B that table 7 is put down in writing, TPE(2), TPE-C, PP(1), polyester, TPE-D, PP(2), polyurethane and TPE-E, then with above-mentioned the same.

Embodiment 61-62

Except making foaming dosage and table 7 is the same, other is the same with embodiment 56.

Embodiment 63-64

As intermediate layer (I) be not to use TPE3, be 0.917g/cm and be to use TPE3 shown in the table 7 and density ³, melt index is the thing that mixes of the low density polyethylene (LDPE) (LLDPE) of 6.5g/10 branch (190 ℃), and is all identical with embodiment 56 in addition.

Embodiment 65

Vacuum has formed not 4 synusia materials of foaming under the following conditions, and foams simultaneously and be shaped.All identical in addition with embodiment 56.

[formation condition]

Heating-up temperature: 380 ℃

Give the hot time: 180 seconds

Vacuum is pressed: 700mmHg

Embodiment 66

[manufacturings of 3 stacked laminates]

Adopted the method lamination same polyamide, TPE-A, TPE3 with embodiment 56.

[the not foaming of foam sheet]

It is to reach 4 minutes in 240 ℃ the air-oven that above-mentioned 3 synusia materials are positioned over temperature, makes TPE(3) not foam sheet foaming is that 30 μ m, TPE-A are that 0.7mm, TPE3 are the 3 synusia materials of 1.0mm thereby make aramid layer.

[manufacturing of lamination formed body]

Above-mentioned 3 synusia materials are carried out preheating, make the aramid layer that constitutes 3 synusia materials be in former one side, by vacuum forming, make it to attract adherence executing on the internal face of die cavity of fine groove pattern that the degree of depth is 150 μ m in former, carry out closing former after the extrusion process, then in this this die cavity of formpiston one side direction the injection moulding filling from the above-mentioned core of the melting attitude of injection molding machine nozzle with thermoplastic elastomer (TPE) [TPE(1) and be cured, at TPE(1) open metal pattern with above-mentioned 3 synusia materials when becoming one, so obtain by 4 layers of lamination formed body that constitutes.

Again, above-mentioned vacuum-formed condition is as follows:

Heating-up temperature: 360 ℃

Preheat the time: 45 seconds

Vacuum is pressed: 700mmHg

In addition, the condition of above-mentioned injection molding forming is as follows:

Forming machine: ィ Na メ Le -(name mechanism is done manufacturing)

Forming temperature: 220 ℃

Injection pressure: once press 100kg/cm ²

Secondary is pressed 700kg/cm ²

Injection speed: maximum

Forming period: 90 seconds/1 cycle

Sprue: direct sprue

(length of shaped segment is 10mm, and wide is 10mm, and thickness is 3mm)

As for so obtain by the aramid layer (top layer) in 4 layers of lamination formed body that constitutes and TPE-A layer [adhesiveness, TPE(3 between intermediate layer (II)) layer [intermediate layer (I] and TPE(1) adhesiveness, fringe depths, soft feeling, abrasion performance, traumatic resistance, oil resistivity, solvent resistance, hear resistance and the cold resistance between layer (sandwich layer), then estimate according to aforementioned evaluation method.

Embodiment 67

Except making the lamination formed body in accordance with the following methods, other is all identical with embodiment 66.

[manufacturing of lamination formed body]

3 synusia materials are carried out preheating, make the aramid layer that constitutes 3 synusia materials be in former one side, make it to attract adherence executing on the internal face of die cavity of candy strip that the degree of depth is 150 μ m by vacuum forming in former, through after the extrusion process, the core of the melting attitude that on 3 synusia materials, distributes equably thermoplastic elastomer (TPE) [TPE(1)], close formpiston, at TPE(1) solidify and open metal pattern with the place that above-mentioned 3 synusia materials become one, thus obtain by 4 layers of lamination formed body that constitutes.

Again, above-mentioned vacuum-formed condition is identical with the vacuum-formed condition of implementing 66.

In addition, the condition of above-mentioned drawing is as follows:

Forming machine: pond shellfish 1 SM-300

Screw diameter: 50mm

Resin temperature: 230 ℃

Moulding pressure: 200kg/cm ²

Forming period: 50 seconds/1 cycle

Formed products: long 500mm, wide 500mm, thick 3mm.

Comparative example 54

Except not using the blowing agent, other is all identical in embodiment 56.

Embodiment 68

[the feed particles TPE(3 of the feed particles TPE-A of intermediate layer (II), intermediate layer (I)) and the feed particles TPE(1 of sandwich layer) manufacturing]

Adopt above-mentioned TPE-A, TPE(3), TPE(1), polyamide, according to the following stated method, made 4 synusia materials.

[manufacturings of 4 layer laminate formed body plates]

At first, Xie Er (Λ Application シ ェ Le) muller is enjoyed in employing, TPE(3 at 100 weight portions) mixes in into 2.0 weight portions as the azodicarbonamide (ADAC) of blowing agent and the cyanuric acid triolefin isopropyl ester (TAIC) of 0.1 weight portion, the T mouth mould extrusion shaper of the 90mm φ that makes with Toshiba then, at full flight screw, L/D=22, extrusion temperature is 180 ℃, and hauling speed is that having made thickness is the not foam sheet of 0.5mm under the condition of 5m/ branch.

Then, adopt that Toshiba makes by 90mm φ, two layers of T mould of crosshead extrusion shaper that 40mm φ constitutes, TPE-A is supplied to the extruder of 90mm φ, polyamide fat (ダ ィ セ Le ヒ ェ Le ス nylon 12L2140) is supplied to the extruder of 40mm φ, under the condition that 220 ℃ of hauling speed 2.5m/ divide, be squeezed into 2 synusia materials then, the then not foam sheet of lamination TPE on the TPE-A that is in the melting attitude that has extruded, making it to pass through between a pair roller, is 30 μ m so make polyamide thickness, the thickness of TPE-A layer is 0.7mm, the thickness of TPE layer is the 3 synusia materials of 0.5mm.

After, adopt the T mouth mould extrusion shaper of the 90mm φ of Toshiba's manufacturing, at extrusion temperature is that 220 ℃, hauling speed are to be squeezed into 2 synusia materials under the 2.5m/ condition of dividing, the then not foaming plate of lamination TPE on the TPE-A that is in the melting shape that has extruded, and make it between a pair roller, to pass through, be that the thickness of 0.7mm, TPE-A layer is that the thickness of 0.7mm, TPE layer is the 3 synusia materials of 0.5mm so make polyamide thickness.

After, adopt the T mouth mould extrusion shaper of the 90mm φ of Toshiba's manufacturing, at extrusion temperature is that 220 ℃, hauling speed are the following TPE(1 of condition that 2.5m/ divides) be squeezed into sheet, and make the tabular TPE(1 that is in the melting attitude that has extruded) contact with not foaming layer one side of the 3 laminate TPE that before made, and make it between a pair roller, to pass through, being that the thickness of 30 μ m, TPE-A layer is that the thickness of 0.7mm, TPE layer is 0.5mm, TPE(1 so make the thickness of aramid layer) thickness of layer is the 4 synusia materials of 3mm.

[the not foaming of foam sheet]

It is to reach 4 minutes in 240 ℃ the air-oven that above-mentioned 4 synusia materials are placed on temperature, so make not foam sheet foaming of TPF, the thickness that finally makes aramid layer is that 30 μ m, TPE-A layer thick is 0.7mm, TPE(3) thickness of layer is 1.0mm, TPE(1) thickness of layer is the 4 synusia materials of 3mm.

[manufacturing of lamination formed body]

Above-mentioned 4 synusia materials are given heat, make the aramid layer that constitutes above-mentioned 4 synusia materials be in former one side, make it to attract the internal face of adherence by vacuum forming, thereby process in air chamber, after this, open metal pattern and just obtained the lamination formed body that constitutes by 4 layers.

Yet above-mentioned vacuum-formed condition is shown below:

Heating-up temperature: 360 ℃

Preheating time: 100 seconds

Vacuum is pressed: 700mmHg

Then, the light that rubs that adopts 60 purpose emery papers the aramid layer surface of this lamination formed body to be carried out 5 minutes.

As for so obtain by adhesiveness, feel, soft feeling, antifriction consumption, traumatic resistance, oil resistivity, solvent resistance, hear resistance between aramid layer (top layer) in 4 layers of lamination formed body that constitutes and the TPE-A layer [intermediate layer (II)], and cold resistance, then estimate according to preceding method.

That estimates the results are shown in table 8.

Embodiment 69-72

Except intermediate layer (II), intermediate layer (I), sandwich layer and the top layer that makes embodiment 68 be shown in the table 8, other is all identical with embodiment 68, thereby has obtained 4 layers lamination formed body.

Evaluation to the lamination formed body that obtained is shown in table 8.

Embodiment 73

Compare with embodiment 68, except not using the TPE(3 of intermediate layer (I)), all made 3 layers lamination formed body in the same manner in embodiment 8.

Evaluation to gained lamination formed body is shown in table 8.

Embodiment 74

In intermediate layer (I), be not to use TPE foam thing, and be to use PP foam thing,, made 3 synusia materials according to the method same with embodiment 68.Make 4 layers lamination formed body then in accordance with the following methods, other way is all identical with embodiment 68.

Above-mentioned 3 synusia materials are carried out preheating, make the aramid layer that has constituted 3 synusia materials be in former one side, and make it to attract to adhere to the internal face of die cavity, close former then, the injection moulding filling, is solidified, at TPE(1 with thermoplastic elastomer (TPE) [TPE(1)] then from the above-mentioned core of the melting attitude of injection molding machine nozzle in the former one side direction die cavity) when becoming one with above-mentioned 3 synusia materials, open metal pattern, thereby obtain by 4 layers of lamination formed body that constitutes.

Again, above-mentioned vacuum-formed condition is as follows.

Heating-up temperature: 360 ℃

Give the hot time: 45 seconds

Vacuum is pressed: 700mmHg

In addition, the condition of above-mentioned extrusion molding is as follows.

Forming machine: ダ ィ Na メ Le -(name mechanism is done manufacturing)

Forming temperature: 220 ℃

Injection pressure: a pressure 1000kg/cm ²

Secondary pressure 700kg/cm ²

Injection moulding speed: maximum

Forming period: 90 seconds/1 cycle

Sprue: direct sprue

(length of shaped segment is 10mm, and wide is 10mm, and thickness is 3mm)

Evaluation to the lamination formed body of gained is shown in table 8.

Embodiment 75

Method (different is the PP foam thing that does not use intermediate layer (I)) according to identical with embodiment 74 has obtained 3 layers lamination formed body.

Evaluation to the lamination formed body of gained is shown in table 8.

Embodiment 76

Made 4 layer laminate formed bodies more in accordance with the following methods after having made 3 synusia materials according to the method identical with embodiment 74, all the other all carry out similarly to Example 8.

Make the aramid layer that constitutes 3 synusia materials be in former one side, make it to attract the internal face of adherence in die cavity, then, on 3 synusia materials, distribute the core be in the melting attitude equably with thermoplastic elastomer (TPE) [TPE(1)], then close former, at TPE(1) solidify and form one with above-mentioned 3 synusia materials in open metal pattern, thereby obtain by 4 layers of lamination formed body that constitutes.

Again, above-mentioned vacuum-formed condition is identical with the vacuum-formed condition of embodiment 74.

In addition, the condition of above-mentioned drawing is as follows:

Forming machine: pond shellfish 1 SM-300

Screw diameter: 500mm φ

Resin temperature: 230 ℃

Moulding pressure: 200kg/cm ²

Forming period: 50 seconds/1 cycle

Formed products: long 500mm, wide 50mm, thickness 3mm.

Embodiment 77

According to the method same with embodiment 76, different is the PP foam thing that does not use embodiment 76 intermediate layers (I), thereby obtains 3 layers lamination formed body.

Evaluation to the lamination formed body of gained is presented at table 8.

Claims (5)

1, a kind of lamination formed body is characterized in that by forming with the lower part:

(a) sandwich layer of forming by synthetic resin;

(b) be arranged on the sandwich layer, by with grafted monomers (that chooses from the group that the derivative of unsaturated carboxylic acid, unsaturated carboxylic acid, unsaturated epoxy monomer and unsaturated carboxylic monomer are formed is at least a) modification the intermediate layer (II) formed of improved polyalkene based elastomers;

(c) top layer of being formed by the a kind of polymer (that chooses from the group that polyamide, polyurethane and polyester are formed is at least a) that is arranged on the intermediate layer (II).

2, a kind of manufacture method of lamination formed body is characterized in that comprising following operation:

The 2 synusia materials of being made up of intermediate layer (II) (elastomer by improved polyalkene system is formed) and top layer (being made of polymer) are carried out preheating, then this 2 synusia material is attracted to be adhered on the mould intracavity wall face of the metal pattern that vacuum forming uses, thereby be formed with the preformed articles of recess;

Make this preformed articles be adhered to above-mentioned vacuum forming with the state of metal pattern mould intracavity wall face or be adhered to above-mentioned vacuum forming with metal pattern be not same, additional forming with the state on the metal pattern mould intracavity wall under, carry out matched moulds, and then obtain having the formed products of recess;

At the recess that is adhered to the formed products on the mould intracavity wall face of above-mentioned metal pattern, inject the synthetic resin that is in the plasticization state that flows, thereby be shaped,

The lamination formed body that makes in the claim 1 to be put down in writing by above-mentioned operation.

3, a kind of manufacture method of lamination formed body is characterized in that comprising following operation:

The 2 synusia materials that are made of intermediate layer (II) (elastomer by improved polyalkene system is formed) and top layer (being made up of polymer) are carried out preheating, then this 2 synusia material is attracted to be adhered to vacuum forming with on the mould intracavity wall face of metal pattern, thereby form preformed articles with recess;

In being adhered to the recess of above-mentioned vacuum forming with the preformed articles on the mould intracavity wall face of metal pattern, perhaps be adhered to above-mentioned vacuum forming be not same, additional forming recess with metal pattern with the preformed articles on the internal face of metal pattern die cavity, charge into the synthetic resin that is in the plasticization state that flows, thereby carry out drawing

The lamination formed body that produces in the claim 1 to be put down in writing by above-mentioned operation.

4, a kind of manufacture method of lamination formed body, it is characterized in that the 3 synusia materials that are made of sandwich layer (being made up of synthetic resin), intermediate layer (II) (being made up of the improved polyalkene based elastomers) and epidermal area (being made up of polymer) are carried out preheating, then, this 3 laminate is carried out vacuum forming, thus 3 laminates of being put down in writing in the acquisition claim 1.

5, a kind of lamination formed body as claimed in claim 1 is characterized in that,

Its surface of described superficial layer (c) is banded by fluffing.

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